JPH093038A - Benzyl sulfide derivative, its production and pest control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new benzyl sulfide derivative exhibiting excellent control effect on various pests and useful as a component of a pesticide. SOLUTION: This compound is expressed by formula I [R<1> is a 1-6C alkyl, etc.; R<2> and R<3> are each independently H or a halogen, etc.; R<4> is H or a halogen, etc.; A is formula II or formula III (R<9> is H or a halogen, etc.; R<10> is H or a 1-4C alkyl; R<11> , R<12> and R<13> are each independently H or cyano, etc.; Q<1> and Q<2> are each N or CR<9> ; (m) is 1, 2 or 3)], e.g. 4-chloro-4'- trifluoromethylsulfonyl-methylbenzophenone-N'-ethoxycarbonylhydrazone. A compound of formula IV in an amount of 1mol is reacted with 1.0-10.0mol of a compound of formula V in the presence of 0-5L of a solvent to obtain an exemplified substance of formula I wherein A is expressed by formula III.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel benzyl sulfide derivative, a method for producing the same, and a pest control agent containing the same as an active ingredient.

[0002]

2. Description of the Related Art The fact that benzohydrazonoylphenyl sulfide derivatives can be used as insecticides has hitherto been known, for example, in US Pat. No. 3,732,307 and JP-A-54-1.
Although it is reported in the specification of JP-A No. 22261 and the specification of JP-A-56-45452, the benzyl sulfide derivative of the present invention has not been known yet.

[0003]

In recent years, existing commercial insecticides have been restricted in use due to problems such as residue, accumulation, environmental pollution, etc., or resistant insects have been generated due to long-term use, and some of them have become less effective. Out. Therefore, it is desired to develop an insecticide having high efficacy even at a low dose and excellent safety.

[0004]

[Means for Solving the Problems] The present inventors have synthesized various benzyl sulfide derivatives and conducted repeated studies on their physiological activities. As a result, the compound of the present invention is various pests, particularly agro-horticultural pests, diamondback moth, lepidopteran pests typified by Spodoptera litura, brown planthopper, leafhopper leafhopper, hemiptera pests typified by cotton aphid and adzuki bean weevils. The present invention has been completed by discovering that it has excellent effects on Coleoptera pests represented by No.

That is, the present invention provides (1) the general formula [I],

[0006]

[Chemical 12] {In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, 1 carbon atom
To C4 cyanoalkyl group, C1 to C4 hydroxyalkyl group, C3 to C6 cycloalkyl group, C1 to C6 haloalkyl group, C2 to C4 alkenyl group, C2 to 4 Alkynyl group, phenyl group [which may be substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms], cyano group, benzyl group [this group may be substituted with a halogen atom], thiazolyl group , An alkylcarbamoyl group having 1 to 4 carbon atoms or -N (R
5) R6 group, wherein R ² and R ³ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An alkylthio group, an alkylcarbonyl group having 1 to 4 carbon atoms, a carboxyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms is shown. R ² and R ³ may form a 3- to 6-membered ring with these bonded carbon atoms. or,
R ¹ and R ² are 3 to 8 having one or more heteroatoms with their attached sulfur and carbon atoms.
You may form a member ring. R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a haloalkoxy group having 1 to 4 carbon atoms, and R ⁵ And R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ together form a group = CR ⁷ R ⁸ or R ⁵ and R ⁶ are 4- to 8-membered rings having one or more heteroatoms in combination with these bonded nitrogen atoms. May be formed. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkylthio group having 1 to 3 carbon atoms, and R ⁸ represents an alkylthio group having 1 to 3 carbon atoms or an alkylamino group having 1 to 3 carbon atoms. R ⁷ and R ⁸ may combine with these bonded carbon atoms to form a saturated or unsaturated 4- to 8-membered ring. A is the formula [A1] or the formula [A
2]

[0007]

Embedded image Represents a hydrazino aralkyl group or a hydrazono aralkyl group, wherein R ⁹ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a carbon atom. An alkoxy group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a haloalkylthio group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, and 2 carbon atoms To 4 alkylsulfonylmethyl group, a haloalkylsulfonyloxy group having 1 to 4 carbon atoms, a phenyl group [the group may be substituted with a halogen atom] or a phenoxy group [the group may be substituted with a halogen atom]. Indicates. Alternatively, two R ^9's may be combined to form a 5- to 6-membered ring. R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms,
Haloalkyl group having 1 to 4 carbon atoms, alkoxyalkyl group having 2 to 10 carbon atoms, alkoxyalkoxyalkyl group having 3 to 8 carbon atoms, alkylthioalkyl group having 2 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, carbon An alkynyl group having 2 to 4 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms, a benzyl group [wherein the group is a halogen atom, 1 to 4 carbon atoms]
Is from haloalkyl groups or 1 carbon atoms substituted by 4 alkyl group may be, group -COR ^14, group -csr ^14,
Group -COOR ^15, group -COSR ^15, group -CON (R
¹⁶ ) R < ¹⁷ >, group-CSN (R < ¹⁶ >) R < ¹⁷ >, group-SN.
^{(R 18) R 19,} group _-SO 2 ^{R 20} or a group -C (R
²¹ ) = CHR ²² is shown. R ¹² and R ¹³ together form a group = CR ²³ R ²⁴ , or R ¹² and R ¹³ are 4 to 8 membered having one or more heteroatoms in combination with their bonded nitrogen atoms. You may form a ring. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, a haloalkoxyalkyl group having 2 to 10 carbon atoms, or 3 to 16 carbon atoms. Alkoxyalkoxyalkyl group, C4-22 alkoxyalkoxyalkoxyalkyl group, C3-6 cycloalkyl group, C1-6 hydroxyalkyl group, C1-6 aminoalkyl group, carbon number An amide alkyl group having 1 to 6 carbon atoms, a cyanoalkyl group having 1 to 8 carbon atoms, an alkoxycarbonylalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a phenyl group [ The group is a halogen atom,
Nitro group, alkyl group having 1 to 4 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, phenoxy group or 1 to 4 carbon atoms
May be substituted with an alkoxy group of), a naphthyl group [the group may be substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms] or a heteroaromatic ring group [the group may have a halogen atom or a carbon number of 1]. To 4 may be substituted with an alkyl group]
R ¹⁵ is an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 2 to 8 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 4 carbon atoms. Group, benzyl group [wherein the group is a halogen atom, an alkoxy group having 1 to 4 carbon atoms or 1 carbon atom]
To 4 may be substituted with an alkyl group] or a phenyl group [wherein the group may be substituted with a halogen atom],
R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group [the group is a halogen atom, a haloalkoxy group having 1 to 4 carbon atoms] Or optionally substituted with an alkyl group having 1 to 4 carbon atoms, and R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 4 carbon atoms (the group being an alkoxycarbonyl group having 1 to 4 carbon atoms). May be substituted with], and is an alkoxyalkyl group having 2 to 5 carbon atoms.
¹⁸ and R ¹⁹ may combine with these bonded nitrogen atoms to form a 5 to 6 membered ring. R ²⁰ represents an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or a dialkylamino group having 2 to 4 carbon atoms, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R
²² represents an alkanoyl group having 2 to 4 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms, R ²³ and R
²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or a group —N (R ²⁵ ) R ²⁶ , and R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a carbon number. An alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, an alkoxyalkyl group having 2 to 12 carbons, or a group-
This shows SO ₂ R ²⁷ . R ²⁵ and R ²⁶ may form a 5- to 6-membered ring together with the nitrogen atom to which they are bonded. R ²⁷ represents an alkyl group having 1 to 8 carbon atoms or a phenyl group [the group may be substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms], and Q ¹ and Q ² represent a nitrogen atom or a group- CR ⁹ is shown, m is 1 or an integer of 2 to 3, and n is 0, 1 or 2. } The benzyl sulfide derivative and its salt represented by these, and (2) General formula [II] which is a novel synthetic intermediate for manufacturing the compound represented by General formula [I],

[0008]

Embedded image {In the formula, R ¹ , R ² , R ³ , R ⁴ , and n have the same meanings as described above, and B is the formula [B1] or the formula [B2].

[0009]

Embedded image Represents an aralkyl group or an arylcarbonyl group represented by, R ⁹ , R ¹⁰ , m, Q ¹ and Q ² have the same meanings as described above, and R ²⁸ represents a halogen atom or a hydroxyl group. } The benzyl sulfide derivative represented by
A general synthetic intermediate [III], which is a novel synthetic intermediate for producing a compound represented by the general formula [I],

[0010]

Embedded image {In the formula, R ⁴ , R ⁹ , R ¹² , R ¹³ , m, Q ¹ and Q
² has the same meaning as described above, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 2
²⁹ represents a halogen atom, a mercapto group or a hydroxyl group. } The benzophenone hydrazone derivative represented by these, (4) General formula [IV],

[0011]

Embedded image {In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , m, n, and Q ¹
And Q ² have the same meaning as described above. } And the compound represented by the general formula [V1],

[0012]

Embedded image {In the formula, R ¹² and R ¹³ have the same meanings as described above. ｝
[Chemical formula 1 characterized by reacting with a compound represented by
A method for producing a benzyl sulfide derivative, wherein A in formula 2 is the formula [A2] in formula 13, (5) general formula [III],

[0013]

Embedded image {In the formula, R ² , R ³ , R ⁴ , R ⁹ , R ¹² , R ¹³ and R
²⁹ , m, Q ¹ and Q ² have the same meanings as described above. } The compound and general formula [V2]

[0014]

Embedded image Z—R ¹ [V2] (In the formula, Z is a halogen atom when R ²⁹ is a mercapto group, an alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group [the group is a methyl group. May be replaced with. ], And when R ²⁹ is a halogen atom, a group-
S (O) nM is shown, and when R ²⁹ is a hydroxyl group, a group -SSR ¹ is shown. R ¹ is an alkyl group having 1 to 6 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or Represents a benzyl group (which may be substituted with a halogen atom), M represents an alkali metal, and n represents 0 or 2. } The compound of the formula 12, characterized by reacting with a compound represented by
A method of producing a benzyl sulfide derivative represented by the formula [A2], wherein (6) the general formula [VI]:

[0015]

[Chemical 21] {In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ , m,
n, Q ¹ and Q ² have the same meanings as described above, and R ²⁸ represents a halogen atom. } And the compound represented by the general formula [V
1],

[0016]

Embedded image {In the formula, R ¹² and R ¹³ have the same meanings as described above. ｝
[Chemical formula 1 characterized by reacting with a compound represented by
A described in 2 is a method for producing a benzyl sulfide derivative represented by the formula [A1] in 13 and (7) a pest control agent containing the benzyl sulfide derivative in 12 as an active ingredient.

In the present specification, the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The alkyl group means a linear or branched alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec. -Butyl group, tert-butyl group, n-pentyl group, isoamyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group, n-heptyl group, n-octyl group, n-nonyl group , N-decyl group and the like.

The cycloalkyl group means a cycloalkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.

The alkenyl group means a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, ethenyl group, 2
-A propenyl group etc. can be mentioned.

The haloalkyl group refers to a linear or branched alkyl group having 1 to 8 carbon atoms, which is substituted with the same or different halogen atoms 1 to 10, for example, a chloromethyl group, a trifluoromethyl group, A tetrafluoroethyl group etc. can be mentioned.

The cyanoalkyl group means a linear or branched alkyl group having 1 to 8 carbon atoms, which is substituted with a cyano group.

The hydroxyalkyl group means a linear or branched alkyl group having 1 to 8 carbon atoms, which is substituted with a hydroxyl group.

The term "alkoxy group" means --O-(alkyl group) in which the alkyl portion has the above meaning, and examples thereof include a methoxy group and an ethoxy group.

The haloalkoxy group means -O- (haloalkyl group) in which the haloalkyl moiety has the above meaning,
For example, a trifluoromethoxy group, a 2-chloroethoxy group, etc. can be mentioned.

The alkylthio group means -S- (alkyl group) in which the alkyl portion has the above-mentioned meaning, and examples thereof include a methylthio group and an ethylthio group.

The haloalkylthio group means -S- (haloalkyl group) in which the haloalkyl moiety has the above meaning, and examples thereof include a trifluoromethylthio group and a 2-chloroethylthio group.

The alkylsulfonyl group means --SO _2- (alkyl group) in which the alkyl moiety has the above meaning,
Examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

The alkylsulfonylmethyl group means -CH ₂ SO _2- (alkyl group) in which the alkyl portion has the above meaning, and examples thereof include a methylsulfonylmethyl group and an ethylsulfonylmethyl group.

The alkoxyalkyl group refers to (alkylene group) -O- (alkyl group) in which the alkyl portion and the alkylene portion have the above meanings, and examples thereof include a methoxymethyl group and an ethoxymethyl group.

The alkylthioalkyl group means (alkylene group) -S- (alkyl group) in which the alkyl portion and the alkylene portion have the above meanings, and examples thereof include a methylthiomethyl group and an ethylthiomethyl group.

The alkoxyalkoxyalkyl group means (alkylene group) -O- (alkylene group) -O- (alkyl group) in which the alkyl portion and the alkylene portion have the above-mentioned meanings.

The term "alkoxyalkoxyalkoxyalkyl group" means that the alkyl moiety and the alkylene moiety have the above meanings (alkylene group) -O- (alkylene group) -O-.
(Alkylene group) -O- (alkyl group) is shown.

The aminoalkyl group means a linear or branched alkyl group having 1 to 8 carbon atoms, which is substituted with an amino group, a monoalkylamino group or a dialkylamino group.

The amidoalkyl group means a linear or branched alkyl group having 1 to 8 carbon atoms, which is substituted with an acylamino group or an N-alkyl-N-acylamino group.

The alkynyl group means a straight chain alkynyl group having 2 to 4 carbon atoms.

The alkylene group means a straight-chain alkylene group having 1 to 8 carbon atoms, and is a methylene group, an ethylene group, a trimethylene group or a tetramethylene group.

The heteroaromatic ring group is a 5-membered aromatic ring group containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms and a condensed ring of these with a benzene ring, or 1 to 3 nitrogen atoms. A 6-membered aromatic ring group containing and a condensed ring thereof with a benzene ring are shown, for example, a furyl group, a thienyl group,
Examples thereof include a pyrazolyl group, an imidazolyl group, a benzofuranyl group, a benzothiazolyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolyl group and a quinoxalinyl group.

The salt in the compound of the present invention means a salt of a compound represented by the general formula [I] and an acid, or a compound represented by the general formula [I], wherein R ² or R ³ is a carboxyl group. Examples of the acid include hydrohalic acids such as hydrochloric acid and hydrobromic acid, or sulfonic acids such as sulfuric acid and methanesulfonic acid, and examples of the metal include sodium and potassium. Examples thereof include alkali metals, alkaline earth metals such as magnesium and calcium, and examples of amines include ammonia, isopropylamine, triethylamine and the like.

In the above general formula [I], R ¹ is preferably an alkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 1 to 2 carbon atoms, a hydroxyethyl group,
A cyclopentyl group, a haloalkyl group having 1 to 2 carbon atoms,
A phenyl group [which may be substituted with a halogen atom], a cyano group, an alkylcarbamoyl group having 1 to 4 carbon atoms or a thiazolyl group, wherein R ² and R ³ are each independently a hydrogen atom or a methyl group. Or, it is an alkoxycarbonyl group having 1 to 2 carbon atoms, and R ¹ and R ² may form a 5-membered ring together with these bonded sulfur atom and carbon atom, and R ⁴ is a hydrogen atom or a fluorine atom. And A is a hydrazinoaralkyl group represented by the formula [A1] or [A2] or a hydrazonoaralkyl group, and R ⁹ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a methyl group,
Trifluoromethyl group, methoxy group, haloalkoxy group having 1 to 2 carbon atoms, methylthio group, difluoromethylthio group, methylsulfonyl group, methylsulfonylmethyl group, trifluoromethylsulfonyloxy group, phenyl group, phenoxy group [the group is May be substituted with a halogen atom] or a methylenedioxy group, R ¹⁰ is a hydrogen atom, R ¹¹ is a hydrogen atom, a group —COR ¹⁴ or a group —COOR ¹⁵ , and R ¹² and R ¹³ are each Independently hydrogen atom, alkyl group having 1 to 4 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, alkoxyalkyl group having 2 to 10 carbon atoms, alkoxyalkoxyalkyl group having 3 to 8 carbon atoms, 2 to 6 carbon atoms An alkylthioalkyl group of
Cyanomethyl group, benzyl group [the group may be substituted with a halogen atom or a trifluoromethyl group], group -CO
R ^14, group -COOR ^15, group -CONHR ^17, a group -
SO ₂ R ²⁰ or a group ^-C (R 21) = a ^{CHR 22, also, R 12} and ^{R 13} together based = ^{CR 23}
R ²⁴ may be formed or R ¹² and R ¹³ may be combined with these bonded nitrogen atoms to form a 5-membered ring, and R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms. , An alkoxyalkyl group having 2 to 6 carbon atoms,
Haloalkoxyalkyl group having 2 to 4 carbon atoms, 3 carbon atoms
To 10 alkoxyalkoxyalkyl groups, 4 carbon atoms
To 12 alkoxyalkoxyalkoxyalkyl groups, cyclopropyl groups, cyanoalkyl groups having 1 to 4 carbon atoms, alkoxycarbonylalkyl groups having 3 to 6 carbon atoms, phenyl groups [these groups being halogen atoms, nitro groups, 1 to 1 carbon atoms 4 may be substituted with an alkyl group, a trifluoromethyl group, a phenoxy group or a methoxy group], a naphthyl group, a pyridyl group, a thienyl group or a 2-furyl group, and R ¹⁵ is an alkyl group having 1 to 10 carbon atoms. , Carbon number 2
6 haloalkyl group, an alkoxyalkyl group or a phenyl group having 2 to 6 carbon atoms, a R ¹⁶ is a hydrogen atom or a methyl group, R ¹⁷ is a hydrogen atom, from 1 to 6 carbon atoms
Is an alkyl group or a phenyl group [which may be substituted with a chlorine atom, a methyl group or a trifluoromethoxy group], R ²⁰ is a methyl group or a trifluoromethyl group, and R ²¹ is a hydrogen atom or a methyl group. R ²² is an acetyl group or a methoxycarbonyl group having carbon atoms, R ^22
23 and R ²⁴ are each independently a hydrogen atom, a chlorine atom,
An alkyl group having 1 to 4 carbon atoms, a 1-triazolyl group or a group —N (R ²⁵ ) R ²⁶ , wherein R ²⁵ and R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
A methoxy group or an alkoxyalkyl group having 2 to 4 carbon atoms, R ²⁷ is an alkyl group having 1 to 4 carbon atoms or a phenyl group [the group may be substituted with a halogen atom or a methyl group], and Q ¹ And Q ² is a nitrogen atom or a group —CR
⁹ , m is 1 or an integer of 2 to 3, and n is R ¹
Is a cyano group or an alkylcarbamoyl group having 1 to 4 carbon atoms, and other than that, a group of compounds represented by 0, 1 or 2 can be mentioned.

In the above-mentioned general formula [II], a preferred group of compounds is that R ¹ is an alkyl group having 1 to 4 carbon atoms,
Cyanomethyl group, hydroxyethyl group, cyclopentyl group, haloalkyl group having 1 to 3 carbon atoms, phenyl group [the group may be substituted with a halogen atom], cyano group, alkylcarbamoyl group having 1 to 4 carbon atoms or thiazolyl group And R ² and R ³ are each independently a hydrogen atom, a methyl group or an alkoxycarbonyl group having 1 to 2 carbon atoms, and R ¹ and R ² together with these bonded sulfur atom and carbon atom are 5 May form a member ring, R ⁴ is a hydrogen atom or a fluorine atom, and B is represented by the formula [B1] or [B
2] which is an aralkyl group or an arylcarbonyl group, wherein R ⁹ is a halogen atom, a trifluoromethyl group,
A methoxy group, a fluoroalkoxy group having 1 to 2 carbon atoms or a phenoxy group [the group may be substituted with a halogen atom], R ¹⁰ is a hydrogen atom, R ²⁸ is a chlorine atom or a hydroxyl group, Q ¹ and Q ² are a nitrogen atom or a group —CR ⁹ , m is an integer of 1 or 2, and n
Is 0 when R ¹ is a cyano group or an alkylcarbamoyl group having 1 to 4 carbon atoms, and other examples include a compound group represented by 0, 1 or 2.

In the general formula [III], preferred compound groups include R ² , R ³ and R ^{4 which} are hydrogen atoms, R ^{9 which} is a 4-substituted chlorine atom, and R ¹² and R ^13.
Is a hydrogen atom, a group -COR ¹⁴ and a group -COOR ¹⁵ ; R ¹⁴ is an alkyl group having 1 to 4 carbon atoms;
¹⁵ is an alkyl group having 1 to 4 carbon atoms, R ²⁹ is a chlorine atom, a mercapto group or a hydroxyl group, and Q ¹
And Q ² is a methine group, and m is a compound group represented by 1.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION Next, general formulas [I], [II],
And typical examples of the compound of the present invention represented by [III] are shown in Tables 1 to 35. The compound numbers will be referred to in the following description.

The compound represented by the general formula [I] has C = N
Since there are two types of geometrical isomers, entgegen (E) isomer and tumen semen (Z) isomer, due to the existence of the bond, the compound of the present invention may be used in the E isomer or Z isomer alone, or as a mixture thereof. it can.

Further, the compound of the present invention represented by the general formula [I] has a tautomer in some cases. For example, group ^{= CR} 23 ^{R 24} is ^{= C (R} 23) -N
In the case of being represented by (R ²⁵ ) R ²⁶ , when R ²⁵ is a hydrogen atom, —N═C (R ²³ ) NH—R as a partial structure.
^The compound having ²⁶ is -NH-C as a partial structure.
It may exist as an equilibrium state of a tautomer having (R ²³ ) ═N—R ²⁶ . Therefore, it should be understood that a compound capable of taking a tautomer in the compound of the present invention has a corresponding tautomer even if the tautomer is not particularly mentioned.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

[0055]

[Table 10]

[0056]

[Table 11]

[0057]

[Table 12]

[0058]

[Table 13]

[0059]

[Table 14]

[0060]

[Table 15]

[0061]

[Table 16]

[0062]

[Table 17]

[0063]

[Table 18]

[0064]

[Table 19]

[0065]

[Table 20]

[0066]

[Table 21]

[0067]

[Table 22]

[0068]

[Table 23]

[0069]

[Table 24]

[0070]

[Table 25]

[0071]

[Table 26]

[0072]

[Table 27]

[0073]

[Table 28]

[0074]

[Table 29]

[0075]

[Table 30]

[0076]

[Table 31]

[0077]

[Table 32]

[0078]

[Table 33]

[0079]

[Table 34]

[0080]

[Table 35]

Next, a method for producing the compound of the present invention will be described.

The compound of the present invention represented by the general formula [I] is
It can be manufactured according to the following manufacturing methods 1 to 5. Manufacturing method 1

[0083]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹² , and R
¹³ , m, n, Q ¹ and Q ² have the same meanings as described above. )

In the production method 1, hydrazines represented by the general formula [V1] or hydrates thereof 1.0 to 10.0 are based on 1 mol of the benzophenones represented by the general formula [IV].
Moles in the presence of 0-5 liters of solvent, if necessary 0.01-
The compound of the general formula [I] is reacted in the presence of 1.0 mol of an acid catalyst.
The compound of the present invention in which A is represented by [A2] can be obtained.

Examples of usable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide. , N-methyl-2
-Aprotic polar solvents such as pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol, ethylene glycol and glycerin, halogenated hydrocarbons such as methylene chloride and chloroform, esters such as ethyl acetate and ethyl propionate. ,
Examples thereof include aliphatic hydrocarbons such as hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, solvents such as acetic acid and water, or a mixed solvent thereof.

Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid monohydrate. Examples thereof include acid addition salts of amines such as pyridine hydrochloride and triethylamine hydrochloride, metal halides such as titanium tetrachloride, zinc chloride, ferrous chloride and ferric chloride, or boron trifluoride / etherate.

The reaction temperature is any temperature from -10 ° C to the reflux temperature in the reaction system, preferably room temperature to 1
50 ° C. The reaction time varies depending on the compound, but can be set between 10 minutes and 20 hours. Manufacturing method 2

[0088]

Embedded image (In the formula, R ² , R ³ , R ⁴ , R ⁹ , R ¹² , R ¹³ ,
m, Q ¹ and Q ² have the same meanings as described above, R ²⁹ represents a halogen atom, Z represents a group MS (O) n, R ¹ has the same meaning as in claim 1, M represents an alkali metal Indicates
n represents 0 or 2. )

In Production Method 2, 1.0 to 3.0 mol of an alkali metal salt of a sulfur compound represented by the general formula [V2] is added to 1 mol of the benzyl halide represented by the general formula [III]. The compound of the present invention in which A is represented by [A2] in the general formula [I] can be obtained by reacting in the presence of a solvent of 0 to 10 l.

Examples of usable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide. , N-methyl-2
-Aprotic polar solvents such as pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol, ethylene glycol and glycerin, halogenated hydrocarbons such as methylene chloride and chloroform, esters such as ethyl acetate and ethyl propionate. ,
Examples thereof include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, solvents such as water, and mixed solvents thereof.

The alkali metal salt of a sulfur compound used in this production method can also be prepared from a sulfur compound in which Z is HS (O) n and an alkali metal, an alkali metal hydride or an alkali metal hydroxide.

The reaction temperature is any temperature from -10 ° C to the reflux temperature in the reaction system, preferably room temperature to 1
50 ° C. The reaction time varies depending on the compound, but can be set between 10 minutes and 20 hours. Manufacturing method 3

[0093]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹² , and R
¹³ , m, Q ¹ and Q ² have the same meanings as described above, and R
²⁹ represents a mercapto group, Z is a halogen atom, an alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group [the group may be substituted with a methyl group. ]. )

In Production Method 3, 1.0 to 5.0 mol of the compound represented by the general formula [V2] was dissolved in 1 to 1 mol of the mercapto compound represented by the general formula [III] in a solvent of 0 to 5 l. The compound of the present invention in which A is represented by [A2] in the general formula [I] can be obtained by reacting in the presence of 0 to 3.0 mol of a base.

Examples of usable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide. , N-methyl-2
Aprotic polar solvents such as pyrrolidone, dimethylsulfoxide and sulfolane, halogenated hydrocarbons such as methylene chloride and chloroform, nitriles such as acetonitrile and propionitrile, esters such as ethyl acetate and ethyl propionate, pentane, Aliphatic hydrocarbons such as hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, and solvents such as water or a mixed solvent thereof can be mentioned.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate and potassium carbonate. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate,
Metal hydrides such as sodium hydride and potassium hydride, alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylamino. Organic bases such as pyridine and 1,8-diazabicyclo [5.4.0] -7-undecene can be mentioned.

The reaction temperature is any temperature from -30 ° C to the reflux temperature in the reaction system, preferably 0 to 150.
° C. The reaction time varies depending on the compound, but is 10 minutes to 2
It can be set between 0 hours. Manufacturing method 4

[0098]

[Chemical formula 26] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹² , and R
¹³ , m, Q ¹ and Q ² have the same meanings as described above, and R
²⁹ represents a hydroxyl group and Z represents the group —SSR ¹ . )

In Production Method 4, 0.1 to 5 is added to 1 mol of the benzyl alcohol represented by the general formula [III].
1.0 in the presence of 1.0 to 3.0 mol of base in 1 solvent, 1.0
To 3.0 mol of diaminochlorophosphine to form a phosphite, and then reacting 1.0 to 5.0 mol of the disulfide represented by the general formula [V2] in the presence of 0 to 5 l of a solvent. The compound of the present invention in which A is represented by [A2] in the formula [I] can be obtained.

As the solvent and the base which can be used, the same ones as in the production method 4 can be mentioned.

The reaction temperature is any temperature from -40 ° C to the reflux temperature in the reaction system, preferably -30 to 5
0 ° C. The reaction time varies depending on the compound, but is 10 minutes to
It can be set between 20 hours. Manufacturing method 5

[0102]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ , and R
¹² , R ¹³ , m, n, Q ¹ and Q ² have the same meanings as described above, R ¹¹ represents a hydrogen atom, and R ²⁸ represents a halogen atom. )

In Production Method 5, 1.0 mol to 1.0 mol of the hydrazine represented by the general formula [V1] or a hydrate thereof is used for 1 mol of the compound represented by the general formula [VI].
The compound of the present invention in which A is represented by [A1] in the general formula [I] can be obtained by reacting in the presence of 5 l of a solvent, if necessary, in the presence of 1.0 to 3.0 mol of a base.

Examples of usable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide. , N-methyl-2
-Aprotic polar solvents such as pyrrolidone, dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as methylene chloride and chloroform, nitriles such as acetonitrile and propionitrile, esters such as ethyl acetate and ethyl propionate, pentane, Solvents such as aliphatic hydrocarbons such as hexane, cyclohexane and heptane, pyridines such as pyridine and picoline and water, and a mixed solvent thereof are included.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate and potassium carbonate. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate,
Metal hydrides such as sodium hydride and potassium hydride, alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylamino. Organic bases such as pyridine and 1,8-diazabicyclo [5.4.0] -7-undecene can be mentioned.

The reaction temperature is any temperature from −30 ° C. to the reflux temperature in the reaction system, preferably 0 to 150.
° C. The reaction time varies depending on the compound, but is 10 minutes to 2
It can be set between 0 hours.

The compound of the present invention represented by the general formula [I] is
The compound of the present invention represented by the general formula [I] itself can be produced as a raw material, and they are shown in the following production methods 6 to 11. However, the method is not limited to these methods. (In the formula, R ³⁰ represents a cyano group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 3 to 8 carbon atoms, carbon Number 2
To C6 alkylthioalkyl group, C2 to C6 alkenyl group, C2 to C4 alkynyl group, benzyl group [the group may be substituted with a halogen atom, a methyl group or a trifluoromethyl group], a group -COR ¹⁴ , group -C
OOR ¹⁵ , group —CON (R ¹⁶ ) R ¹⁷ , group —SN
^{(R 18) R 19,} group _-SO 2 ^{R 20,} a group -C
(R < ²¹ >) = CHR < ²² > or the group -C (R < ²³ >) = NR.
^25, and when R ³⁰ is a group —C (R ²¹ ) ═CHR ²² , X ¹ is a halogen atom, a hydroxyl group, or a carbon number of 1 to 1.
A C4 alkoxy group, a C1-4 alkylcarbonyloxy group, a mercapto group, a C1-4 alkylthio group, a C1-4 alkylsulfonyloxy group or a benzenesulfonyloxy group (the group being a methyl group. May be substituted), and in other cases, a halogen atom, an alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group [the group may be substituted with a methyl group. ]. In ^{addition, R} 30 -X ¹ is together, R
^It may be ¹⁷ NCO or ClSO ₂ NCO.
R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ , R ¹¹ , R
¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R
¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R
²⁵ , Q ¹ , Q ² , m and n have the same meanings as described above. ) That is, the compound of the present invention [VII], [IX] or [XI]
1.0 to 10.0 mol of the compound represented by the general formula [V3] is added to 1 mol of the compound shown in the presence of 0 to 5 l of a solvent, if necessary, 0.1 to 3.0 mol of an acid or base. By reacting in the presence of a new compound of the present invention [VII
I], [X] or [XII] are obtained.

As the solvent and the acid catalyst which can be used, the same ones as in the production method 1 can be mentioned.

Examples of the base include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, sodium carbonate, potassium carbonate and the like. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate,
Metal hydrides such as sodium hydride and potassium hydride, alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylamino. Organic bases such as pyridine and 1,8-diazabicyclo [5.4.0] -7-undecene can be mentioned.

The reaction temperature is any temperature from -30 ° C to the reflux temperature in the reaction system, preferably 0 to 150.
° C. The reaction time varies depending on the compound, but is 10 minutes to 2
It can be set between 0 hours.

When the chlorosulfonyl isocyanate is reacted with the above-mentioned compound [VII], [IX] or [XI], the reaction product is then isolated or hydrolyzed without isolation to give R ^The compound of the present invention in which ³⁰ is represented by CONH ₂ can be obtained. Manufacturing method 6

[0112]

Embedded image (In the formula, R ³⁰ represents a cyano group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a carbon number of 2 to 1
0 alkoxyalkyl group, C 3-8 alkoxyalkoxyalkyl group, C 2-6 alkylthioalkyl group, C 2-6 alkenyl group, C 2-4 alkynyl group, benzyl group [the group halogen atoms may be substituted with a methyl group or a trifluoromethyl group], groups -COR ^14, a group -COOR ^15, a group -C
Indicates ON ^{(R 16)} R ^17, group ^{-SN (R 18)} R ^19, group _-SO 2 ^{R 20,} group ^-C (R 21) = ^{CHR 22,} or a group ^{-C (R 23) = NR 25} , R ³⁰ is a group -C (R
²¹ ) = CHR ²² , X ¹ is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
An alkylcarbonyloxy group, a mercapto group, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group (the group may be substituted with a methyl group), and In this case, a halogen atom, an alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group [the group may be substituted with a methyl group. ]. Further, R ³⁰ -X ¹ may be integrated into R ¹⁷ NCO or ClSO ₂ NCO. R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ , R
¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R
¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , and R
²³ , R ²⁵ , Q ¹ , Q ² , m and n have the same meanings as described above. )

That is, the compounds of the present invention [VII], [IX]
Alternatively, the compound of the general formula [V
3] to 0 to 5 l of a compound of 1.0 to 10.0 mol
The compound of the present invention [VIII], [X] or [XII] is obtained by reacting in the presence of the solvent of 1), if necessary, in the presence of 0.1 to 3.0 mol of an acid or a base.

As the solvent and the acid catalyst which can be used, the same ones as in the production method 1 can be mentioned.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate and potassium carbonate. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate,
Metal hydrides such as sodium hydride and potassium hydride, alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylamino. Organic bases such as pyridine and 1,8-diazabicyclo [5.4.0] -7-undecene can be mentioned.

The reaction temperature is any temperature from −30 ° C. to the reflux temperature in the reaction system, preferably 0 to 150.
° C. The reaction time varies depending on the compound, but is 10 minutes to 2
It can be set between 0 hours.

When the chlorosulfonyl isocyanate is reacted with the above-mentioned compound [VII], [IX] or [XI], the reaction product is then isolated or hydrolyzed without isolation to give R ^The compound of the present invention in which ³⁰ is represented by CONH ₂ can be obtained. Manufacturing method 7

[0118]

[Chemical 29] (In the formula, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group —N (R ²⁵ ) R ^26. R ¹ , R ² , R ³ , and R ⁴ , R ⁹ , R ¹⁰ ,
R ¹¹ , m, n, Q ¹ and Q ² have the same meanings as described above, and R ²⁵ and R ²⁶ each independently represent an alkyl group having 1 to 4 carbon atoms. X ² represents an alkoxy group having 1 to 4 carbon atoms. Alternatively, two X ² and carbon may be combined to form a carbonyl group. )

That is, for 1 mol of the compound of the present invention compound [XIII] or [XIV], the compound of the general formula [V
4] and the compound (1.0-10.0 mol)
The compound of the present invention [XV] or [XVI] can be obtained by reacting in the presence of the solvent, if necessary, in the presence of 0.01 to 1.0 mol of an acid catalyst and a solvent.

This reaction can be carried out under the same conditions as in production method 1. Manufacturing method 8

[0121]

Embedded image (In the formula, R ³³ is an azolyl group or a group —N (R ²⁵ ) R
²⁶ , and R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ²⁵ ,
R ²⁶ , m, n, Q ¹ and Q ² have the same meanings as described above, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X ³ represents a chlorine atom or a bromine atom. )

That is, with respect to 1 mol of the compound represented by the compound [XVII] of the present invention, 1.0 ^ 10.0 mol of a halogenating agent is reacted in the presence of a solvent of 0 to 5 l to prepare a new compound of the present invention. Compound [XVIII] is obtained. Then, 1.0 to 5.0 mol of the compound represented by the general formula [V5] is reacted in a solvent of 0 to 5 l in the presence of 1.0 to 3.0 mol of a base, if necessary. Compound [XX] is obtained. The compound [XX] of the present invention can also be obtained by using a compound represented by the general formula [XIX] instead of the compound [XVIII].

Examples of the halogenating agent include phosphorus pentachloride, thionyl chloride, a mixture of triphenylphosphine / carbon tetrachloride and triphenylphosphine / bromine. Examples of usable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, halogenated hydrocarbons such as methylene chloride and chloroform, acetonitrile and propio. Examples thereof include nitriles such as nitrile, solvents such as pentane, hexane, cyclohexane, and aliphatic hydrocarbons such as heptane, or a mixed solvent thereof. The halogenating agent can also serve as a solvent.

The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably 10 to 180 ° C.
It is. The reaction time varies depending on the compound, but it is 10 minutes to 20 minutes.
Can be set between times.

Compound [XIX] can be obtained by reacting compound [XVII] with phosphorus oxychloride. Specific examples of this reaction are described in, for example, Chemical Abstracts, Vol. 113, 97192b.

The compound [XX] of the present invention has the general formula [XVI:
II] or [XIX] is usually obtained by reacting with a compound of the general formula [V5] in the presence of a solvent, if necessary, in the presence of a base and a catalyst.

As the solvent and the base which can be used, the same ones as in the production method 6 can be mentioned. As the catalyst, a sulfinate salt such as sodium methanesulfinate or sodium p-toluenesulfinate or a hydrate thereof can be used. The reaction temperature is any temperature from 0 ° C to the reflux temperature in the reaction system, preferably 10 to 100 ° C. The reaction time varies depending on the compound, but can be set between 10 minutes and 20 hours. Manufacturing method 9

[0128]

[Chemical 31] (In the formula, n represents 1 or 2, A, R ¹ , R ² , R ³ ,
R ⁴ and l have the same meanings as described above. )

That is, with respect to 1 mol of the compound represented by the compound [XXI] of the present invention, 1.0 to 10.0 mol of an oxidizing agent is added in the presence of 0 to 5 l of a solvent, if necessary, 0.01 to 1. 0
A new compound of the present invention [XXII] is obtained by reacting in the presence of a molar amount of a catalyst.

Examples of the oxidizing agent include hydrogen peroxide and m-
Chloroperbenzoic acid, sodium periodate, Oxone (trade name of OXONE, E. I. Dupont; containing potassium hydrogen peroxosulfate), N-chlorosuccinimide, N-bromosuccinimide, hypochlorous acid tert.
-Butyl ester, sodium hypochlorite and the like. Examples of the catalyst include sodium tungstate.

Examples of the solvent that can be used here include ethers, aromatic hydrocarbons, aprotic polar solvents, alcohols, halogenated hydrocarbons and aliphatic hydrocarbons as used in Production Method 1. , Acetic acid, water and ketones such as acetone, methyl ethyl ketone and cyclohexanone, or a mixed solvent thereof.

The reaction temperature is any temperature from −20 ° C. to the reflux temperature in the reaction system, preferably 10 to
100 ° C. The reaction time depends on the compound, but it is 10
It can be set between minutes and 20 hours. Manufacturing method 10

[0133]

Embedded image (In the formula, R ² and R ³ each independently have 1 to 4 carbon atoms.
Or an haloalkyl group having 1 to 3 carbon atoms, and A, R ¹ , R ⁴ and n have the same meanings as described above. X
⁴ represents a halogen atom, an alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group [the group may be substituted with a methyl group]. )

That is, with respect to 1 mol of the compound represented by the general formula [XXIII], 0 to 5 l of a solvent and 1.0 to 3.0 are used.
The compound is reacted with 1.0 to 5.0 mol of an alkylating agent represented by the general formula [V6] in the presence of a molar base, and the compound of the general formula [XX
IV] can be produced. The compound [XXIV] is then isolated or without isolation in the presence of 0-5 liters of solvent and 1.0-3.0 moles of base, an alkylating agent of the general formula [V7] 1. 0 to
A compound represented by the general formula [XXV] can be produced by reacting with 5.0 mol.

As the base and solvent which can be used in these reactions, for example, the same ones used in the production method 6 can be mentioned. The reaction temperature is any temperature from -30 ° C to the reflux temperature in the reaction system, preferably 0-100 ° C. Manufacturing method 11

[0136]

[Chemical 33] (In the formula, X ⁴ represents a halogen atom, an alkylsulfonyloxy group having 1 to 4 carbon atoms, or a benzenesulfonyloxy group [the group may be substituted with a methyl group].
R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ , R ¹¹ , R
¹² , R ¹³ , Q ¹ , Q ² , m and n have the same meanings as described above. )

That is, the compound of the present invention [XXVI] or [X
XVIII] to 1 mol of the compound represented by the general formula [V
8] The salt of the compound of the present invention [XVII] or [XIX] can be obtained by reacting the acid of the present invention in the presence of a solvent of 1.0 to 3.0 mol 0.1 to 5 l.

As the solvent which can be used in these reactions, for example, the same solvent as used in the production method 1 can be mentioned. The reaction temperature is any temperature from -30 ° C to the reflux temperature in the reaction system, preferably 0-10.
0 ° C.

The novel synthetic intermediates represented by the above general formulas [II] and [III] are, for example, the following Production Method 12
-It can manufacture according to the manufacturing method 20. Manufacturing method 12

[0140]

Embedded image (In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number 1
A haloalkyl group of -6, a phenyl group [the group may be substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms], a benzyl group [the group may be substituted with a halogen atom] or a thiazolyl group. X ⁴ is a halogen atom,
An alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group [the group may be substituted with a methyl group], M ¹ represents an alkali metal, and M ² represents an alkali metal or an ammonium ion. R ² , R ³ ,
R ⁴ , m, Q ¹ and Q ² have the same meanings as described above. n represents 1 or 2. )

That is, with respect to 1 mol of the benzyl halide represented by the general formula [XXX], 1.0 to 3.0 mol of the alkali metal salt of sulfinic acid represented by the general formula [V9] is added to 0 to 10 l of the solvent. In the presence of the general formula [X
XXI] can be obtained.

Examples of the solvent that can be used here include ethers, aromatic hydrocarbons, aprotic polar solvents,
Examples thereof include alcohols, halogenated hydrocarbons, aliphatic hydrocarbons and water, or a mixed solvent thereof. The reaction temperature is any temperature from 0 ° C to the reflux temperature in the reaction system, preferably 10 to 100 ° C.

The sulfinates used in this case can be used as reagents or by known methods [for example, Journal of Chemical Society (J. Chem. Soc.), No. 63].
Volume 6 (1945) or Journal of American Chemical Society (JA Chem. So).
c. ), 96, No. 7, 2275 (1974)
Year)) method].

Under the same reaction conditions, compound [XXX]
From the thiocyanate represented by the general formula [V10], the compound represented by the general formula [XXXII] can be obtained.

Further, mercaptans of the general formula [V11] 1.0 to 3.
0 mol can be reacted in the presence of 1.0 to 0.3 mol of a base in a solvent of 0 to 5 l to obtain a sulfide represented by the general formula [XXXIII].

As the solvent and the bases, for example, the production method 6 can be used.
The same thing as is mentioned. The reaction temperature is any temperature from −10 ° C. to the reflux temperature in the reaction system, preferably 0 to 100 ° C.

The thus obtained compound [XXXI
II] With respect to 1 mol, 1.0 to 10.0 mol of an oxidizing agent is added in the presence of 0 to 5 l of a solvent, if necessary, 0.01 to 1.0.
The compound of the present invention [XXXIV] is obtained by reacting in the presence of a molar amount of a catalyst.

Examples of the oxidizing agent include hydrogen peroxide and m-
Chloroperbenzoic acid, sodium periodate, Oxone (OXONE, trade name of E. I. DuPont; potassium hydrogen peroxosulfate-containing), N-chlorosuccinimide, N-bromosuccinimide, hypochlorous acid tert.
-Butyl or sodium hypochlorite and the like can be mentioned. Examples of the catalyst include sodium tungstate.

Examples of the solvent that can be used here include ethers, aromatic hydrocarbons, aprotic polar solvents, alcohols, halogenated hydrocarbons and aliphatic hydrocarbons as used in Production Method 1. , Acetic acid, water and ketones such as acetone, methyl ethyl ketone and cyclohexanone, or a mixed solvent thereof.

The reaction temperature is any temperature from −20 ° C. to the reflux temperature in the reaction system, preferably 10 to
100 ° C.

The benzyl halides represented by the general formula [XXX], which are the starting materials for production, are generally known, or known methods [for example, organic synthesis (Org.S.
ynth. ), Vol. 4, p. 921 (1963)], the methyl group of the corresponding arylcarbonyltoluene is converted into a halogenating agent (for example, chlorine, bromine,
It can be obtained by halogenation with N-chlorosuccinimide, N-bromosuccinimide, sulfuryl chloride or sulfuryl bromide).

Arylcarbonyltoluene is generally
It can be obtained by reacting with an arylcarboxylic acid halide in toluene in the presence of a Lewis acid such as aluminum chloride. Manufacturing method 13

[0153]

Embedded image (In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, and 3 to 3 carbon atoms.
6 cycloalkyl group, C1-6 haloalkyl group, C1-4 cyanoalkyl group or C1-4
Is a hydroxyalkyl group, Rf is a fluorine atom or a perfluoroalkyl group, X ⁴ is a halogen atom,
An alkylsulfonyloxy group having 1 to 4 carbon atoms or a benzenesulfonyloxy group [the group may be substituted with a methyl group] is shown. R ² , R ³ , R ⁴ , m, Q ¹ and Q ² have the same meanings as described above. n represents 1 or 2. )

General formula [XXXIII] or [XXXV
III] has the general formula [XXX
V] to 1 mol of benzyl mercaptan represented by
1.0 to 3.0 mol of an alkylating agent represented by the general formula [V12], dibenzothiophenium trifluoromethanesulfonates represented by the general formula [XXXVI] or perfluoroalkenes represented by the [XXXVII], In the presence of 0-10 l of solvent, if necessary 1.0-
It can be obtained by reacting in the presence of 3.0 mol of base.

As the base and the solvent that can be used here,
For example, the same one as used in the production method 6 can be mentioned. The reaction temperature is any temperature from 0 ° C to the reflux temperature in the reaction system, preferably 10 to 150 ° C.
It is.

The thus obtained general formula [XXXI
II] or [XXXVIII] can be oxidized by the same oxidation method as in the production method 12 to obtain the corresponding sulfoxide and sulfone derivative.

The benzyl mercaptans represented by the general formula [XXXV] as a raw material for production are already known, or known methods such as organic synthesis (Org.S).
ynth. ), Vol. 3, page 363 (1955)] or in accordance therewith. That is,
It can be obtained by reacting the benzyl halide represented by the general formula [XXX] as a raw material of the production method 12 with sodium hydrosulfide or by reacting thiourea with a base in the presence of a base and then hydrolyzing it. Manufacturing method 14

[0158]

Embedded image (In the formula, R ¹ , R ⁴ , R ⁹ , m, n, Q ¹ and Q ² have the same meanings as described above. R ² and R ³ represent an alkyl group or a haloalkyl group, and X ⁴ represents a halogen atom. , Carbon number 1
~ 4 alkylsulfonyloxy group or benzenesulfonyloxy group [wherein the group may be substituted with a methyl group. ]
Is shown. )

That is, to 1 mol of the compound represented by the general formula [XXXIX], 0 to 5 l of solvent and 1.0 to 3.0 are used.
In the presence of a molar base, the general formulas [V13] and [V1
4] is reacted with 1.0 to 5.0 moles of the alkylating agent represented by the formula 4) in the same manner as in the production method 10 to obtain the compounds represented by the general formulas [XL] and [XL].
I] can be produced. Also, X
⁴ is present in the side chain of the R ¹ group, R ¹ and R ²
With these attached sulfur and carbon atoms form a 3- to 8-membered ring having one or more heteroatoms.

As the base and the solvent which can be used here,
For example, the same one as used in the production method 6 can be mentioned. The reaction temperature is any temperature from 0 ° C to the reflux temperature in the reaction system, preferably 10 to 150 ° C.
It is. Manufacturing method 15

[0161]

Embedded image (In the formula, R ⁴ , R ⁹ , m, n, Q ¹ and Q ² have the same meanings as described above. R ¹ represents an alkyl group or a haloalkyl group.)

That is, with respect to 1 mol of the compound of the present invention represented by the general formula [XLII], the carbanion represented by the general formula [XLIII] 1.0 to
The compound represented by the general formula [XLIV] can be produced by reacting with 5.0 mol. General formula [XLIII]
The method for generating the carbanion represented by 1) is 1) 1.
0 to 15.0 mol of trihalomethane and 1.0 to 15.0
A method in which a mol base is contacted in the presence of 0.01 to 1.0 mol of a tetraalkylammonium salt, a benzyltrialkylammonium salt, a tetraalkylphosphonium salt, and a crown ether or the like phase transfer catalyst, if necessary 2). Method of contacting 1.0 to 15.0 mol of (trialkylsilyl) alkyl halide with 1.0 to 15.0 mol of hydrogen fluoride salt such as potassium fluoride or tetrabutylammonium fluoride and 3 ) 1.0
~ 5.0 moles of alkyl halide or haloalkyl halide, 1.0 to 5.0 moles of lithium, sodium,
A method of contacting with a metal such as copper or zinc or an organometallic compound such as lithium diisopropylamide, phenyllithium or butyllithium can be mentioned. Examples of the solvent that can be used here include ethers, aromatic hydrocarbons, aprotic polar solvents, alcohols, aliphatic hydrocarbons, ethers, aromatic hydrocarbons, aprotic polar solvents, alcohols. , Aliphatic hydrocarbons and water, or a mixed solvent thereof.

The reaction temperature is any temperature from -70 ° C to the reflux temperature in the reaction system, preferably -50.
５０50 ° C. Manufacturing method 16

[0164]

Embedded image (In the formula, R ² , R ³ , R ⁴ , R ⁹ , m, n, Q ¹ and Q
² has the same meaning as described above. X ⁵ represents halogen, cyano or the group SR ¹ . R ¹ represents an alkyl group or a haloalkyl group. )

That is, with respect to 1 mol of the compound of the present invention represented by the general formula [XLV], 0-5 liter of solvent and 1.0-5.
The compound of the general formula [XLVI] is reacted with 1.0 to 5.0 mol of the compound of the general formula [XLVI] in the presence of 0 mol of a base.
VII] can be produced. Examples of the base and solvent that can be used here include production method 6
The same thing as used in can be mentioned.

The reaction temperature is any temperature from -70 ° C to the reflux temperature in the reaction system, preferably -50.
５０50 ° C. Manufacturing method 17

[0167]

Embedded image (In the formula, R ¹ , R ⁴ , R ⁹ , m, n, Q ¹ and Q ² have the same meanings as described above.)

That is, usually, in the presence of a solvent and a base, 1.0 to 3.0 mol of a base in 0.1 to 5 l of a solvent is added to 1 mol of benzyl alcohol represented by the general formula [XLVIII]. In the presence of 1.0 to 3.0 mol of dialkylaminochlorophosphines to form a phosphite, then disulfides of general formula [V15] 1.0 to 3.0
The compound of the present invention represented by the general formula [XLIX] can be obtained by reacting 5.0 mol of the compound in the presence of 0 to 5 l of a solvent.

Examples of usable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide. , N-methyl-2
-Aprotic polar solvents such as pyrrolidone, dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as methylene chloride and chloroform, nitriles such as acetonitrile and propionitrile, esters such as ethyl acetate and ethyl propionate, pentane, Solvents such as aliphatic hydrocarbons such as hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, and mixed solvents thereof can be mentioned.

Examples of the base include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, sodium carbonate, potassium carbonate and the like. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate,
Metal hydrides such as sodium hydride and potassium hydride, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8
Examples include organic bases such as diazabicyclo [5.4.0] -7-undecene.

The reaction temperature is any temperature from -40 ° C to the reflux temperature in the reaction system, preferably -30 to 5
0 ° C. The reaction time varies depending on the compound, but is 10 minutes to
It can be set between 20 hours. Manufacturing method 18

[0172]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ ,
Q ¹ , Q ² , M ³ , m and n have the same meanings as described above. )

That is, the compound [L] of the present invention was added to 1.0 to 5.0 mol of a reducing agent in the presence of 0 to 5 l of a solvent and, if necessary, 0.01 to 1.0 mol of a catalyst. Or by reacting with 1.0 to 5.0 mol of the alkyl metal compound represented by the general formula [V16].
The compound of the present invention of I] can be obtained.

Examples of the reducing agent include hydrogen molecules, sodium borohydride, lithium aluminum hydride, diisobutylaluminum hydride and the like. Examples of the catalyst include platinum, nickel, cobalt and palladium.

Examples of the solvent that can be used here include ethers, aromatic hydrocarbons, aprotic polar solvents, alcohols, aliphatic hydrocarbons, acetic acid, water, and mixed solvents thereof.

The reaction temperature is any temperature from -20 ° C to the reflux temperature in the reaction system, preferably 10-
100 ° C. The reaction time depends on the compound, but it is 10
It can be set between minutes and 20 hours. Manufacturing method 19

[0177]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ ,
Q ¹ , Q ² , m and n have the same meanings as described above. X ³ represents a chlorine atom or a bromine atom. )

With respect to 1 mol of the compound [LI] of the present invention, 1.
By reacting 0 to 10.0 mol of a halogenating agent in the presence of 0 to 5 l of a solvent, a new compound of the present invention [LI
I] is obtained.

As the halogenating agent, hydrogen chloride, hydrogen bromide, phosphorus trichloride, phosphorus tribromide, thionyl chloride, triphenylphosphine / carbon tetrachloride and triphenylphosphine /
Examples thereof include a mixture of bromine. Examples of usable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, halogenated hydrocarbons such as methylene chloride and chloroform,
Nitriles such as acetonitrile and propionitrile,
Solvents such as pentane, hexane, cyclohexane, and aliphatic hydrocarbons such as heptane, and mixed solvents thereof can be mentioned. The halogenating agent can also serve as a solvent.

The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably 10 to 180 ° C.
It is. The reaction time varies depending on the compound, but it is 10 minutes to 20 minutes.
Can be set between times. Manufacturing method 20

[0181]

Embedded image (In the formula, R ² , R ³ , R ⁴ , R ⁹ , R ¹² , R ¹³ , and R
²⁹ , Q ¹ , Q ² , and m have the same meanings as described above. )

That is, to 1 mol of the benzophenone represented by the general formula [LIII], 1.0 to 10.0 mol of the hydrazine represented by the general formula [V1] or a hydrate thereof is added to 0 mol.
The compound of the present invention represented by the general formula [III] can be obtained by reacting in the presence of ˜5 l of solvent, if necessary in the presence of 0.01 to 1.0 mol of acid catalyst.

As the solvent and the acid catalyst which can be used here, for example, the same ones as used in the production method 1 can be mentioned.

The reaction temperature is any temperature from −10 ° C. to the reflux temperature in the reaction system, preferably 0 to 1
00 ° C.

[0185]

EXAMPLES Next, the production method, formulation method and use of the compound of the present invention will be specifically described with reference to examples.

Production Example 1 Production of 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenone-N′-ethoxycarbonylhydrazone (Compound No. I-175) 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenone (0 0.5g) and ethyl-carbazate (0.4g) were added to ethanol (60ml) and acetic acid (5g).
ml) and stirred under reflux for 19 hours. The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue is subjected to silica gel column chromatography (n-hexane: ethyl acetate = 4: 1).
, And the desired product (0.6 g, melting point 148-150)
C., yield 96%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.30 (3H, t) 4.23 (2H, q) 4.35, 4.53 (2H, s, s) 7.03 to 7.80 (9H, m)

Production Example 2 4-Chloro-4'-methylsulfonylmethylbenzophenone-hydrazone (Compound No.
Preparation of I-2) 4-chloro-4′-methylsulfonylmethylbenzophenone (10.0 g) and hydrazine monohydrate (4.9).
g) to ethanol (200 ml) and acetic acid (10 ml)
In addition, the mixture was stirred under reflux for 6 hours. The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to obtain the desired product (10.0 g, melting point 52-54 ° C., yield 9).
7%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.73, 2.85 (3H, s, s) 4.20, 4.30 (2H, s, s) 5.50 (2H, br) 7.05 to 7.70 (8H, m)

Production Example 3 Production of 4-chloro-4′-methylsulfonylmethylbenzophenone-N′-propionylhydrazone (Compound No. I-15) 4-chloro-4′-methylsulfonylmethylbenzophenone-hydrazone (1.3 g) , Propionyl chloride (0.4 g) and potassium carbonate (0.7 g) were added to a solvent of ethyl acetate (150 ml) and water (100 ml), and the mixture was stirred at room temperature for 2 hours. The reaction mixture was separated, the ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and the ethyl acetate was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2:
Purified in 1), the desired product (1.3 g, melting point 159-16)
0 ° C., yield 86%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.23 (3H, t) 2.85 to 3.00 (5H, m) 4.30 (2H, s) 7.00 to 8.00 (8H, m) 8.25 (1H, br)

Production Example 4 Production of 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenone-hydrazone (Compound No. I-136) 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenone (2.5 g), hydrazine Monohydrate (4.3 g) and p-toluenesulfonic acid monohydrate (0.2 g) were added to ethanol (30 ml), and the mixture was stirred under reflux for 3 hours. The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (n-
The product was purified with hexane: ethyl acetate = 2: 1) to obtain the desired product (2.2 g, n _D ²⁰ 1.5871, yield 85%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.43, 4.53 (2H, s, s) 5.47, 5.53 (2H, s, s) 7.07 to 7.60 (8H, m)

Preparation Example 5 Preparation of 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N-propionylhydrazone (Compound No. I-149) 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone-hydrazone (0 .9 g), propionyl chloride (0.22 g) and potassium carbonate 0.4 g
Was added to a solvent of ethyl acetate (100 ml) and water (100 ml), and the mixture was stirred at room temperature for 16 hours. The reaction mixture was separated, the ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and the ethyl acetate was evaporated under reduced pressure. The solid residue was washed with n-hexane to obtain the desired product (0.75 g, melting point 13
0-132 ° C, yield 75%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.20 (3H, t) 2.60 to 3.00 (2H, m) 4.47 (2H, d) 7.03 to 7.63 (8H, m) 8.22 (1H, d)

Production Example 6 4-Chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N '-(1
-Chloropropylidene) hydrazone (Compound No. II-1
4) Preparation of 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N'-propionylhydrazone (1.7 g), triphenylphosphine (1.5 g) and carbon tetrachloride (1.2 g) in acetonitrile (80 m).
1) and stirred under reflux for 10 minutes. The reaction mixture is concentrated and the residue is subjected to silica gel column chromatography-
Purify with (n-hexane: ethyl acetate = 10: 1),
Target product (1.7 g, melting point 108-109 ° C., yield 97
%) Was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.05, 1.10 (3H, t, t) 2.50, 2.55 (2H, q, q) 4.47 (2H, s) 7.00-7.85 (8H, m)

Production Example 7 4-Chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N '-[1
Preparation of-(1H-1,2,4-triazol-1-yl) propylidene] hydrazone (Compound No. II-10) 4-Chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N '-(1-chloropropyiene Redden)
Hydrazone (1.0 g), 1H-1,2,4-triazole (0.2 g), potassium carbonate (0.4 g) and p-
Sodium toluenesulfinate (0.3 g) was added to N, N
-In addition to dimethylformamide (70 ml) 95-1
The mixture was stirred at 00 ° C for 7 hours. After cooling to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 1) to obtain the desired product (0.7 g, n _D ²⁰ 1.5978, yield 6).
6%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.28 (3H, t) 3.28 (2H, q) 4.52 (2H, s) 7.05 to 7.86 (8H, m) 7.95 (1H, s) 8.40, 8.52 (1H, s, s)

Production Example 8 4-Chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N '-[1
Preparation of-(N-methylamino) ethylidene] hydrazone (Compound No. II-8) 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N '-(1-chloroethylidene) hydrazone (0.7 g) and 40 % Methylamine aqueous solution (0.3 g) was added to xylene (50 ml), and the mixture was stirred under reflux for 1 hour. The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to obtain the desired product (0.6
g, melting point 58-60 ° C., yield 87%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.00, 2.20 (3H, s, s) 2.67, 2.94 (3H, d, d) 4.46 (2H, s) 6.30 (1H, br) 6.95- 7.78 (8H, m)

Production Example 9 Production of 4-chloro-4′-ethylsulfonylmethylbenzophenone-N′-isopropylidenehydrazone (Compound No. II-35) 4-chloro-4′-ethylsulfonylmethylbenzophenonehydrazone (0.7 g) Was added to acetone (30 ml), and the mixture was stirred under reflux for 30 minutes. The reaction mixture was concentrated to give the desired product (0.7 g, n _D ²⁰ 1.6163, yield 88
%) Was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.34 (3H, t) 2.00 (6H, s) 2.90 (2H, q) 4.20 (2H, s) 7.00 to 7.67 (8H, m)

Production Example 10 4-Chloro-4'-methylthiomethylbenzophenone-N '-[1- (N, N-dimethylamino) ethylidene] hydrazone (Compound No. II-
22) Preparation of 4-chloro-4′-methylthiomethylbenzophenone-
Hydrazone (2.0 g) and dimethylacetamide-dimethylacetal (1.4 g) were added to ethanol (100 m).
1) and stirred under reflux for 6 hours. The reaction mixture was concentrated and extracted with ethyl acetate. After washing the ethyl acetate layer with water,
It was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 1),
Light yellow transparent viscous liquid target product (2.0 g, yield 81%)
I got ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.00 (3H, s) 2.35 (3H, s) 2.88 (6H, s) 3.66, 3.70 (2H, s, s) 7.03 to 7.75 (8H, m)

Preparation Example 11 Preparation of 4-chloro-4′-methylsulfonylmethylbenzophenone-semicarbazone (Compound No. I-42) 4-chloro-4′-methylsulfonylmethylbenzophenone-hydrazone (1.3 g) and chlorosulfonylisocyanate Nato (0.63 g) was added to ethyl acetate (100 m
l) and stirred at room temperature for 1 hour, then water (100 m
1) was added, and the mixture was further stirred at room temperature for 16 hours. The reaction mixture was separated, the ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and the ethyl acetate was evaporated under reduced pressure. The solid residue was washed with a mixed solvent of ethyl acetate: n-hexane = 4: 1 to obtain the desired product (1.2 g, melting point 189 to 191 ° C.,
(80% yield). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.87, 2.97 (3H, s, s) 4.34, 4.50 (5H, m) 7.10 to 7.70 (8H, m)

Production Example 12 4-Chloro-4'-methylthiomethylbenzophenone-N'-ethoxycarbonyl-
Preparation of N'-methylhydrazone (Compound No. I-47) 4-chloro-4'-methylthiomethylbenzophenone-
N'-Ethoxycarbonylhydrazone (4.3 g) was dissolved in N, N-dimethylformamide (100 ml), 60% sodium hydride (0.6 g) was added to this solution, and the mixture was stirred at room temperature for 30 minutes and then iodinated. Methyl (2.
5 g) was added and the mixture was stirred at room temperature for 16 hours. Water was added to the reaction mixture, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 5: 1) to obtain the desired product (4.3 g, n _D ²⁰ 1.6042, yield 8).
9%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.17 (3H, t) 2.00 (3H, s) 2.79, 3.00 (3H, s, s) 3.63, 3.67 (2H, s, s) 4.04 ( 2H, q) 7.07 to 7.57 (8H, m)

Production Example 13 Production of 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenone-4-butylsemicarbazone (Compound No. I-171) 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenonehydrazone ( 1.2 g), triethylamine (0.5 g) and butyl isocyanate (0.6 g)
g) was added to tetrahydrofuran (30 ml), and the mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with 2N hydrochloric acid and water, dried over anhydrous magnesium sulfate, and ethyl acetate was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain the desired product (0.6 g, melting point 179-181 ° C., yield 40%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 0.75 to 1.65 (7H, m) 3.15 to 3.50 (2H, m) 4.50 (2H, s) 6.20 (1H, br) 6.90 to 7.70 ( 9H, m)

Production Example 14 4-Chloro-4′-trifluoromethylsulfonylmethylbenzophenone-N′-methylsulfonyliminomethylhydrazone (Compound No. I
-137) Preparation of 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone hydrazone (1.2 g), triethylamine (1.6 g) and ethyl N-methylsulfonylformimidate (1.2 g) in dioxane (30 ml). In addition, the mixture was stirred under reflux for 5 hours. Concentrate the reaction mixture,
The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to obtain the desired product (0.
8g, melting point 63-65 ° C, yield 52%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.95, 3.05 (3H, s, s) 4.45, 4.60 (2H, s, s) 4.95 (1H, br) 7.10-7.80 (8H, m) 8.80 (1H, br)

Production Example 15 Production of 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone-N'-methylsulfonylhydrazone (Compound No. I-182) 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenonehydrazone ( 1.2 g) and triethylamine (0.4 g) were dissolved in ethyl acetate (30 ml) and to this solution was added methanesulfonyl chloride (0.4 g).
g) was added dropwise at room temperature and stirred for 1 hour. The reaction mixture was washed with 2N hydrochloric acid and water, dried over anhydrous magnesium sulfate, and ethyl acetate was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain the desired product (0.5 g, melting point 64).
˜65 ° C., yield 36%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 3.50 (3H, s) 4.50 (2H, d) 7.10 to 7.70 (9H, m)

Preparation Example 16 Preparation of 4-chloro-4′-methylsulfinylmethylbenzophenone-N′-propionylhydrazone (Compound No. I-14) 4-chloro-4′-methylthiomethylbenzophenone-
N'-propionylhydrazone (0.8 g) and sodium periodate (0.5 g) were added to methanol (50 ml).
And water (7 ml), and the mixture was stirred at room temperature for 16 hours.
The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 9: 1) to obtain the desired product (0.7 g, melting point 153).
˜156 ° C., yield 84%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.21 (3H, t) 2.43, 2.56 (3H, s, s) 2.85 (2H, q) 3.93, 4.00 (2H, s, s) 6.96- 7.70 (8H, m) 8.23 (1H, br)

Production Example 17 4-Chloro-4 '-(2-methylsulfonyl-2-propyl) benzophenone-N'
-Hexanoyl-N'-methylhydrazone (compound number
I-248) Preparation 4-chloro-4'-methylsulfonylmethylbenzophenone-N'-hexanoylhydrazone (1.4 g), methyl iodide (5.6 g) and 60% sodium hydride (0.15 g) were added. N, N-dimethylformamide (80
ml) and stirred at room temperature for 16 hours. Water was added to the reaction mixture and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to obtain the desired product (0.8 g, melting point 94-96 ° C., yield 53).
%) Was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 0.90 (3H, m) 1.10 to 1.93 (6H, m) 1.87 (6H, s) 2.16 to 2.67 (2H, m) 2.57, 2.76 ( 3H, s) 3.09 (3H, s) 7.05 to 7.73 (8H, m)

Production Example 18 Synthesis of 4-chloro-4′-trifluoromethylsulfonylmethylbenzhydrylhydrazine (Compound No. V-8) Toluene (80 ml) was mixed with hydrazine monohydrate (50 m).
1) and 4-chloro-4′-trifluoromethylsulfonylmethylbenzhydryl chloride were added and gradually heated with stirring. The mixture was stirred at 80 ° C for 2 hours, allowed to cool, and then poured into water. Add 250 ml of ethyl acetate and extract,
After washing with water and drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the desired product as a pale yellow candy-like substance (2.9
g, n _D ²⁰ 1.5671, yield 82.4%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 3.83 (2H, br) 4.38 (2H, s) 4.83 (1H, s) 6.93 to 7.50 (8H, m)

Production Example 19 N- (4-chloro-4'-trifluoromethylsulfonylmethylbenzhydryl)-
Synthesis of N'-methoxycarbonylhydrazine hydrochloride (Compound No. V-13) N- (4-chloro-4'-trifluoromethylsulfonylmethylbenzhydryl) -N'-methoxycarbonylhydrazine 1.6 g in methanol 80 ml In addition, 3 ml of hydrochloric acid was added with stirring at room temperature. It was gradually heated to reflux. After stirring under reflux for 2 hours, it was allowed to cool. The solvent was distilled off under reduced pressure, and the target substance as a pale yellow powder (1.6 g, melting point 52-54 ° C, yield 91.5) was obtained.
%) Was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 3.6 (3H, s) 4.73 (2H, s) 5.23 (1H, s) 7.27 to 7.50 (8H, m)

Production Example 20 Production of 4-chloro-4'-ethylthiomethylbenzophenone-N'-ethoxycarbonylhydrazone (Compound No. I-114) 1.2 g of ethanethiol and 1 g of sodium hydroxide were added to N, N-dimethylformamide. After suspending in (50 ml), 3.5 g of 4-chloro-4′-chloromethylbenzophenone-N′-ethoxycarbonylhydrazone was added, and the mixture was stirred at room temperature for 16 hours. Water was added to the reaction mixture, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n- hexane: ethyl acetate = 4: 1) purified by then the desired product ^{_{(2.0g, n D 20 1.6198,}} 53% yield). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.34 (6H, t) 2.53 (2H, q) 3.70, 3, 80 (2H, s, s) 4.25 (2H, q) 7.10-7.77 (8H, m)

Production Example 21 Production of 4-chloro-4'-difluoromethylthiomethylbenzophenone-N'-methoxycarbonylhydrazone (Compound No. I-187) 4-chloro-4'-mercaptomethylbenzophenone-
N'-methoxycarbonylhydrazone (1.5 g) and potassium hydroxide (1.5 g) were added to dioxane (30 ml).
Dichloromethyl chloride was bubbled into this solution at 40 ° C. until the starting material 4-chloro-4′-mercaptomethylbenzophenone-N′-methoxycarbonylhydrazone disappeared. The reaction mixture was cooled to room temperature and then filtered. The organic layer of the filtrate was dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain the desired product (0.3 g, n _D ²⁰ 1.
6213, yield 18%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 3.78 (3H, s) 3.98, 4, 10 (2H, s, s) 6.7, 6.8 (1H, t) 7.07 to 7.67 (8H, m) 7. 77 (1H, s)

Production Example 22 Production of 4-chloro-4'-methylthiomethylbenzophenone-N'-methoxycarbonylhydrazone (Compound No. I-67) 4-chloro-4'-hydroxylmethylbenzophenone-N'-methoxycarbonylhydrazone ( 1.2 g) and triethylamine (0.5 g) are added to tetrahydrofuran (30 ml), and chlorobisdiethylaminophosphine (1.1 g) is added dropwise to this solution at -20 ° C. After stirring at room temperature for 2 hours, the solvent was evaporated under reduced pressure, ice water and ethyl acetate were added, and the layers were separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain phosphite. This was added to tetrahydrofuran (30 ml) and added to this solution at 0 ° C.
Dimethyl disulfide (g) was added dropwise with and the mixture was further stirred at room temperature for 12 hours. After confirming that the raw material phosphite had disappeared, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate =
4: 1) and the desired product (0.3 g, melting point 40-4)
2 ° C., yield 17%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.93, 2.08 (3H, s, s) 3.67, 3.77 (2H, s, s) 3.8 (3H, s) 7.1 to 7.67 (8H, m) 7.85 (1H, br)

Production Example 23 Production of 4-chloro-4′-methylsulfonylmethylbenzophenone (Compound No. VI-3) 4-bromomethyl-4′-chlorobenzophenone (3.
1 g) and sodium methanesulfinate (1.5 g)
Was added to N, N-dimethylformamide (50 ml),
The mixture was stirred at room temperature for 16 hours. Water was added to the reaction mixture, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n-hexane to obtain the desired product (2.
8 g, melting point 164-166 ° C., yield 90%) were obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.90 (3H, s) 4.47 (2H, s) 7.37 to 7.83 (8H, m)

Preparation Example 24 Preparation of 4-chloro-4′-ethylsulfonylmethylbenzophenone (Compound No. VI-6) Sodium sulfite (24.5 g) and sodium hydrogen carbonate (33 g) were dissolved in water (200 ml), and Ethanesulfonyl chloride (25 g) was added to the solution at room temperature over 30 minutes, and the mixture was stirred for 1 hour. The reaction mixture was concentrated and the residue was washed with N, N-dimethylformamide (200 m).
After suspending in l), 4-bromomethyl-4′-chlorobenzophenone (10.0 g) was added, and the mixture was stirred at room temperature for 16 hours. Water was added to the reaction mixture, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n-hexane to obtain the desired product (7.5 g, melting point 11).
7-118 ° C., yield 72%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.37 (3H, t) 2.93 (2H, q) 4.27 (2H, s) 7.20 to 7.83 (8H, m)

Production Example 25 Production of 4-chloro-4′-ethylthiomethylbenzophenone (Compound No. VI-4) 4-chloro-4′-mercaptomethylbenzophenone (16.0 g), ethyl bromide (7.4 g) and Potassium hydroxide (4.3 g) was added to methanol (250 ml), and the mixture was stirred under reflux for 30 minutes. The reaction mixture was cooled to room temperature and then concentrated. Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over anhydrous magnesium sulfate and concentrated. The residue is subjected to silica gel column chromatography (n-hexane: ethyl acetate = 10: 1).
And purified with the desired product (14.0 g, melting point 33 to 34 ° C.,
(79% yield). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.23 (3H, t) 2.45 (2H, s) 3.75 (2H, s) 7.10 to 7.90 (8H, m)

Production Example 26 4-chloro-4′-difluoromethylthiomethylbenzophenone (Compound No. VI-1
Preparation of 5) 4-chloro-4'-mercaptomethylbenzophenone (14.7 g) and potassium hydroxide (15 g) were added to a solvent of dioxane (100 ml) and water (100 ml),
Difluoromethyl chloride was blown into this solution at 60 ° C. for 1 hour until the starting material 4-chloro-4′-mercaptomethylbenzophenone was consumed. The reaction mixture was cooled to room temperature and then filtered. The organic layer of the filtrate was dried over anhydrous magnesium sulfate and concentrated. The residue is subjected to silica gel column chromatography (n-hexane: ethyl acetate = 5: 1).
The desired product (6.4 g, melting point 34-35 ° C., yield 36%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.03 (2H, s) 6.69 (1H, t) 7.15 to 7.71 (8H, m)

Production Example 27 Production of 4-chloro-4′-difluoromethylsulfonylmethylbenzophenone (Compound No. VI-16) 4-chloro-4′-difluoromethylthiomethylbenzophenone (3.2 g) and m-chloroperbenzoic acid. (5.
3 g) was added to chloroform (150 ml), and this suspension was stirred under reflux for 3 hours. The reaction mixture was concentrated, water was added to the residue, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue solid was washed with n-hexane to obtain the desired product (2.7 g, melting point 154-157 ° C., yield 7).
8%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.57 (2H, s) 6.41 (1H, t) 7.27 to 7.87 (8H, m)

Production Example 28 4-Chloro-4'-trifluoromethylthiomethylbenzophenone (Compound No. VI-
Preparation of 12) 4-Chloro-4′-mercaptomethylbenzophenone (4.5 g) was dissolved in tetrahydrofuran (150 ml), and 60% sodium hydride (0.8 g) was added to this solution.
Was added, the mixture was stirred at room temperature for 30 minutes, S- (trifluoromethyl) dibenzothiophenium-trifluoromethanesulfonate (6.4 g) was added, and the mixture was further stirred for 30 minutes. The reaction mixture was concentrated, water was added thereto, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain the desired product (2.0
g, melting point 63-65 ° C., yield 35%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.14 (2H, s) 7.30 to 7.77 (8H, m)

Production Example 29 4-chloro-4 ′-(1,
Preparation of 1,2,2-tetrafluoroethylthiomethylbenzophenone (Compound No. VI-20) 4-Chloro-4'-mercaptomethylbenzophenone (5.0 g) and potassium tert-butoxide (0.9 g) were added to ethanol. (150 ml), and perfluoroethylene (2.9 g) was blown into the mixture at room temperature, followed by stirring for 16 hours. The reaction mixture was filtered and concentrated, and the residue was subjected to silica gel column chromatography- (n-
The product was purified with hexane: ethyl acetate = 4: 1) to obtain the desired product (5.3 g, melting point 48-50 ° C., yield 77%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.13 (2H, s) 5.77 (1H, tt) 7.23 to 7.73 (8H, m)

Production Example 30 Production of 4-chloro-4′-methylthiomethylbenzophenone (Compound No. VI-1) 4-bromomethyl-4′-chlorobenzophenone (3.
1 g) and 15% methyl mercaptan-sodium aqueous solution (5.6 g) were added to methanol (150 ml), and the mixture was stirred under reflux for 30 minutes. The reaction mixture was concentrated and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure.
The residual solid was washed with n-hexane to obtain the desired product (2.3
g, melting point 59-61 ° C., yield 83%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.00 (3H, s) 3.70 (2H, s) 7.13 to 7.74 (8H, m)

Production Example 31 4-Chloro-4′-methylsulfinylmethylbenzophenone (Compound No. VI-2)
Preparation of 4-chloro-4′-methylthiomethylbenzophenone (4.2 g) was added to methanol (150 ml), sodium periodate (3.6 g) dissolved in water (20 ml) was added to this solution, and the mixture was stirred at room temperature. Stir for 16 hours. The reaction mixture was concentrated, water was added thereto, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n-hexane to give the desired product (4.1 g, melting point 116).
˜118 ° C., yield 93%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ value) 2.50 (3H, s) 4.00 (2H, s) 7.30 to 7.80 (8H, m)

Production Example 32 4- (3-bromopropyl)
Production of Sulfonylmethyl-4′-chlorobenzophenone (Compound No. VI-11) 4- (3-Bromopropyl) thiomethyl-4′-chlorobenzophenone (5.1 g) and 31% hydrogen peroxide solution (6 g) were added to acetic acid ( 200 ml), and the mixture was stirred at 80 ° C. for 1 hour and further refluxed for 1 hour. The reaction mixture was concentrated, water was added thereto, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with aqueous potassium carbonate solution and water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure.
The residual solid was washed with n-hexane to obtain the desired product (5.0
g, melting point 105-107 ° C., yield 91%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.17 to 2.60 (2H, m) 3.00 to 3.17 (2H, m) 3.53 (2H, t) 4.33 (2H, s) 7.23 to 7.87 ( m, 8H)

Production Example 33 4-chloro-4 ′-(1,1
Preparation of -dioxothiolan-2-yl) benzophenone (Compound No. VI-36) 4- (3-Bromopropyl) sulfonylmethyl-4'-
Chlorobenzophenone (2.5 g) and 60% sodium hydride (0.3 g) were added to N, N-dimethylacetamide (70 ml), and the mixture was stirred at room temperature for 16 hours. Water was added to the reaction mixture, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue is subjected to silica gel column chromatography (n-hexane: ethyl acetate = 1: 1).
To obtain the target product (1.0 g, yield 50%) as a pale yellow candy-like substance. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.67 to 2.73 (4H, m) 2.87 to 3.33 (2H, m) 4.02 to 4.37 (1H, m) 7.23 to 7.97 (8H, m)

Production Example 34 Production of 4-chloro-4 ′-(2-trifluoromethylsulfonylpropyl) benzophenone (Compound No. VI-28) 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenone (3.3 g) And 60% sodium hydride (0.8 g) were added to N, N-dimethylacetamide (1
50 ml) and stirred at room temperature for 1 hour, methyl iodide (0.8 g) was added to the solution, and the mixture was stirred at room temperature for 16 hours. Water was added to the reaction mixture, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain the desired product (3.1 g, melting point 107-109 ° C., yield 86%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.00 (6H, s) 7.20 to 7.70 (8H, m)

Production Example 35 Production of 4-chloro-4′-thiocyanatomethylbenzophenone (Compound No. VI-35) 4-Bromomethyl-4′-chlorobenzophenone (5.
7 g) and sodium thiocyanate (5.5 g) were added to ethanol (50 ml), and the mixture was stirred at 60 ° C for 1 hr.
The reaction mixture was concentrated, water was added to the residue, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residual solid was washed with a mixed solvent of n-hexane: ethyl acetate = 10: 1 to obtain the desired product (2.2 g, melting point 129 to 131 ° C., yield 42%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.18 (2H, s) 7.23 to 7.87 (8H, m)

Production Example 36 Production of diethyl 2- {4- (4-chlorobenzoyl) phenyl} -2-trifluoromethylthiomalonate (Compound No. VI-80) 60% sodium hydride (0.5 g) was added to tetrahydrofuran ( 150 ml) and stirred at 0 ° C. under stirring 2- {4
Diethyl-(4-chlorobenzoyl) phenyl} malonate (4.4 g) was added dropwise. 0 after hydrogen generation stops
Trifluoromethylsulfenyl chloride was blown thereinto at 0 ° C, and then the mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated, water was added to the residue, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 8:
1) and the desired product (4.7 g, n _D ²⁰ 1.536)
2, yield 87%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.3 (6H, t) 4.35 (4H, q) 7.4 (2H, d) 7.75 (2H, d) 7.8 (4H, s)

Production Example 37 4-chloro-4′-trichloromethylthiomethylbenzophenone (Compound No. VI-8
Preparation of 1) 4-chloro-4'-thiocyanic acid methylbenzophenone (5.5 g) and triethylbenzylammonium chloride (0.5 g) were dispersed in chloroform (30 ml), and a 48% sodium hydroxide aqueous solution (4 ml) was added at 40 ° C.
After that, the mixture was stirred as it was for 3 hours.

Cold water was added, the layers were separated, the organic phase was washed with water and dried over magnesium sulfate, and then chloroform was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 9: 1 mixed solution) to obtain the desired product (1.0 g, melting point 103 to 105 ° C., yield 13%) ¹ H-NMR data. (60 MHz, CDCl ₃ solvent, δ
Value) 4.45 (2H, s) 7.15 to 7.8 (8H, m)

Production Example 38 Production of 4-chloro-4′-trifluoromethylsulfonylmethylbenzhydrol (Compound No. VIII-2) 4-chloro-4′-trifluoromethylsulfonylmethylbenzophenone (5.5 g) was added to methanol. (200m
l), and sodium borohydride was gradually added to this while stirring at room temperature, and the mixture was further stirred at room temperature overnight.
After completion of the reaction, methanol was distilled off under reduced pressure. After the residue was extracted with 250 ml of ethyl acetate, it was washed with water,
After drying with magnesium sulfate, ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 2: 1 mixed solution) to obtain the desired product as a white powder (4.2 g, melting point 113-115 ° C., yield 77%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.7 (2H, s) 5.77 (2H, s) 7.3 (4H, s) 7.47 (4H, s)

Production Example 39 4-Chloro-4'-ethanesulfonylmethylbenzhydryl chloride (Compound No. VI
Preparation of II-5) 4-Chloro-4′-ethanesulfonylmethylbenzhydrol (6.0 g), thionyl chloride (5.4 g), 200 ml of toluene and a catalytic amount of N, N-dimethylformamide were added and stirred. While gradually heating to reflux. The mixture was stirred under reflux for 4 hours, allowed to cool, and the solvent was evaporated under reduced pressure. The residue is subjected to silica gel column chromatography (developing solvent hexane: ethyl acetate = 2: 1 mixed solution).
The target product of a light yellow candy-like substance (4.6 g,
n _D ²⁰ 1.6044, yield 75%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 1.33 (3H, t) 2.88 (2H, q) 4.37 (2H, s) 6.05 (1H, s) 7.27 (4H, s) 7.35 (4H, s)

Production Example 40 Production of (6-chloro-3-pyridyl) (4-trifluoromethylthiomethylphenyl) ketone (Compound No. VII-3) (6-chloro-3-pyridyl) (4-thiocyanatomethyl) Phenyl) ketone (5.0 g) was dissolved in tetrahydrofuran (300 ml), trifluoromethyltrimethylsilane (5.0 g) was added at room temperature, and then cooled to 5 ° C. Tetrabutylammonium fluoride (1.0M
Tetrahydrofuran solution (23 g) was gradually added dropwise under cooling, and the mixture was stirred as it was overnight. After tetrahydrofuran was distilled off under reduced pressure, the residue was extracted with ethyl acetate. This was washed with water and dried over magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure. The residue is subjected to silica gel column chromatography (developing solvent hexane: ethyl acetate = 4: 1 mixed solution).
The product of interest (yield 2.0 g, n _D ²⁰ 1.58)
20, yield 35%) was obtained. ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 4.15 (2H, s) 7.4 (3H, dd) 7.72 (2H, dd) 8.05 (2H, dd) 8.67 (2H, d)

Production Example 41 Production of 4-chloro-4′-hydroxymethylbenzophenone-N′-methoxycarbonylhydrazone (Compound No. IX-1) 4-chloro-4′-hydroxymethylbenzophenone (0.5 g) and methyl- Carbazate (0.4 g) was added to ethanol (60 ml) and acetic acid (5 ml), and the mixture was stirred under reflux for 19 hours. The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain the desired product (0.5 g, yield 83%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value) 2.17 (1H, br) 3.77 (3H, s) 4.63, 4.73 (2H, s, s) 6.97 to 7.63 (8H, m) 7.73 (1H, br)

When the compound of the present invention is used as an active ingredient of a pest control agent, the compound of the present invention may be used as it is, but a carrier, a surfactant, or a carrier generally used for formulation as an agrochemical adjuvant, And other auxiliary agents are mixed to prepare emulsions, suspensions, powders, granules, tablets, wettable powders, aqueous solutions, liquids, flowables, wettable granules, aerosols,
It can be formulated into various forms such as pastes, oils and emulsions. The mixing ratio of these is usually 0.1 active ingredient.
.About.90 parts by weight and 10 to 99.9 parts by weight of the agricultural chemical adjuvant.

[0229] The carriers used for formulation herein are classified into solid carriers and liquid carriers. As the solid carrier, for example, starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal, powdered animal or vegetable powder such as milk powder, talc, kaolin,
Bentonite, calcium carbonate, zeolite, diatomaceous earth,
Mineral powders such as white carbon, clay and alumina can be used. Examples of the liquid carrier include water, alcohols such as isopropyl alcohol and ethylene glycol,
Ketones such as cyclohexanone and methyl ethyl ketone,
Dioxane, ethers such as tetrahydrofuran, kerosene, aliphatic hydrocarbons such as light oil, xylene, trimethylbenzene, tetramethylbenzene, methylnaphthalene, aromatic hydrocarbons such as solvent naphtha, halogenated hydrocarbons such as chlorobenzene, Examples thereof include acid amides such as dimethylacetamide, esters such as glycerin ester of fatty acid, nitriles such as acetonitrile, and sulfur-containing compounds such as dimethyl sulfoxide.

Examples of the surfactant include alkylbenzene sulfonic acid metal salt, dinaphthylmethane disulfonic acid metal salt, alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkyl. Examples include aryl ethers and polyoxyethylene sorbitan monoalkylates.

Other auxiliary agents include, for example, carboxymethyl cellulose, gum arabic, sodium alginate, guar gum, tragacanth gum, polyvinyl alcohol and other fixing agents or thickeners, metal soap and other defoaming agents,
Physical property improvers such as fatty acids, alkyl phosphates, silicones and paraffins, colorants and the like can be used.

In the actual use of these preparations, they can be used as they are or diluted with a diluent such as water to a predetermined concentration. Application of various preparations containing the compound of the present invention, or a dilution thereof, is a generally applied application method, that is, spraying (for example, spraying, misting, atomizing, dusting, granulation, water surface application, box application). Etc.), soil application (for example, mixing, irrigation, etc.), surface application (for example, application, dressing, coating, etc.), dipping, poison bait and the like. It is also possible to feed the livestock with the above-mentioned active ingredient mixed with feed to control the generation and growth of harmful insects, especially harmful insects, in the excrement thereof. It can also be applied by a so-called ultra-high concentration small amount application method. In this method, it is possible to contain 100% of the active ingredient.

Application of the pest control agent of the present invention is generally 0.1 to 50000 ppm, preferably 1 to 10000.
Perform at an active ingredient concentration of ppm.

The concentration of the active ingredient can be appropriately changed depending on the form of the preparation, the method of application, the purpose, the time, the place, the state of generation of pests and the like. For example, in the case of aquatic pests, it can be controlled even by spraying a drug solution having the above concentration range to the place of occurrence, so the concentration range of the active ingredient in water is the above or less.
The amount applied per unit area is 0.1 to 5000 g, preferably 1 to 1000 g as an active ingredient compound per ha.
Are used, but are not limited thereto.

Needless to say, the compound of the present invention is sufficiently effective alone, but if necessary, other fertilizers, pesticides such as insecticides, acaricides, nematicides, fungicides, and antibacterial agents are used. It can be mixed and used in combination with a virus agent, an attractant, a herbicide, a plant growth regulator and the like, and in this case, a more excellent effect may be exhibited.

Typical examples of insecticides, fungicides, acaricides and the like which can be used by mixing with the compound of the present invention are shown below.

For example, organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon,
Chlorpyrifos, oxydeprophos, bamidothion, fentoate, dimethoate, formothion, malathion, trichlorfon, thiomethone, phosmet, dichlorvos, acephate, EPBP, methylparathion,
Oxydimethone methyl, ethione, dioxabenzophos, cyanophos, isoxathion, pyridafenthion, phosalone, methidathion, sulprophos, chlorfenbinphos, tetrachlorovinphos, dimethylbinphos, propaphos, isofenphos, disulfoton, profenophos, pyraclofos, monocrotophos, Azinphos-methyl, aldicarb, mesomil, thiodicarb, carbofuran, carbosulfan, benfulacarb, fratiocarb, propoxur, fenobucarb, metolcarb, isoprocarb, carbaryl, pirimicarb, ethiophencarb, diclofenthion, pirimiphosmethyl, quinalphos, chlorpyrifosmethyl, prothiophos, nared, nared, nared, Iocarb, oxamyl, alanical , Such as chlorobutyl host.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrine, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, etholin. Fenprox, cycloprothrin, tralomethrin, silafluofen, tefluthrin, bifenthrin, acrinathrin, etc.

Acyl urea-based and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron,
Triflumuron, teflubenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, rufenuron, cyromazine, methoprene, endosulfan, diafenthiuron, imidacloprid, fipronil, nicotine sulfate, rotenone, methaaldehyde, machine oil, BT and insects Microbial pesticides such as pathogenic viruses, phenoxycarb, cartap, thiocyclam,
Bensultap, tebufenozide, chlorfenapyr,
Emamectin benzoate, acetamiprid, nitenpyram, pymetrozine, sodium oleate, rapeseed oil, etc.

Nematicides: fenamiphos, fosthiazate, etoprophos, methyl isothiocyanate, 1,3
-Dichloropropene, DCIP and the like.

Acaricides: chlorbenzilate, phenisobromolate, dicofol, amitraz, propargite, benzomate, hexithiazox, fenbutatin oxide, polynactin, quinomethionate, chlorfensone, tetradiphone, abamectin, milbemectin, clofentezine, pyridaben. , Fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor, etoxazole, halfenprox, etc.

Fungicides: thiophanate methyl, benomyl, carbendazole, thiabendazole, folpet, thiuram, ziram, zineb, manneb, manzeb,
Polycarbamate, iprobenphos, edifenphos,
Fusalide, probenazole, isoprothiolane, chlorothalonil, captan, polyoxin, blasticidin S, kasugamycin, streptomycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil, flutolanil, penciclone,
Iprodione, Hymexazole, Metalaxyl, Triflumizole, Triphorine, Triadimefon, Vitertanol, Fenalimol, Propiconazole, Simoxanil, Prochloraz, Pefurazoate, Hexaconazole, Microbutanyl, Diclomedine, Tecloftalam,
Propineb, dithianon, fosetyl, vinclozolin,
Procymidone, oxadixyl, guazatine, propamocarb hydrochloride, fluazinam, oxolinic acid, hydroxyisoxazole, imibenconazole, difenoconazole, mepanipyrim and the like.

The compounds of the present invention are used for hemiptera pests, lepidopteran pests, coleopteran pests, diptera pests, hymenoptera pests, orthoptera pests, termite pests, thrips pests, spider mites and plant parasites. It shows an excellent control effect against harmful insects such as sex nematodes. Examples of such pests include the following pests.

Hemiptera pests, such as the beetle bug (R
iptortus clavatus), southern green stink bug (Nezara viridula), stink bug (Lygus sp.), American beetle stink bug (Blissusleucopterus),
Nasigumbai (Stephanitis nashi)
Stink bugs (Heteroptera; HETEROPTERA),
Nephotettix cinc
rice, rice leafhoppers (Empoasca)
sp. , Erythroneura sp. , Cir
culifer sp. ) Such as leafhoppers, brown planthoppers (Nilaparvata lugens), and sedge planters (Sogatella furcifer)
a), Larvae plant, Laodelphax str
plants such as iatellus), Psylla s
p. And other whiteflies, Bemisi tabaci (Bemisi)
atabaci), Whitefly Whitefly (Triale)
Whiteflies such as urodes vapororium, Vineus aphid
folii), green peach aphid (Myzus pe)
rsicae), apple aphid (Aphis po)
mi), Aphis gossypii
i), Aphis fabae, Rhopalosiphum psedoboras
sicas), Potato aphid (Aul)
aphids such as Acorthum solani) and Schizophis graminum, Pseudoc
occus comstocki), ruby weevil (Ceroplastes rubens), San Jose pea insect (Comstockockaspis per)
niciosa), the scale insect (Unaspi)
syannonsis) and other scale insects, as well as Triggered turtles (Rhodnius sp.) and the like.

Lepidopteran pests such as chamomaki (Homo
na magnanima)
oxophies orana), Tenguhamaki (Sp
arganothis pilleriana), Nasihimeshingui (Grapholitha molest)
a), Legume minivoragl
ycinivorella), codling moth (Laspe)
yresia pomonella), Eucosma
sp. , Lobesia botrana, etc., Grape biloba (Eupoecilia a)
Mbiguella) and other leaf tortoises, Bamba
lina sp. And other minnows, Nempo (Nemapo)
gon granellus, iga (Tineat)
ranslucens, etc., Lymenetia prunifolia
a) and other leafminers, P. sylvestris (Phyllo)
lycaenidae such as norycter rigoniella, citrus fruit moth (Phyllocnistis)
Citrella, etc., Plutella xylostella, Plutella xylostella (Pl.)
utella xylostella), Plays
Stags such as citri, grape mosquito (Parant)
hrene regalis), Synanthedo
n sp. Etc., etc., Cotton bollworm (Pec)
Tinophora gossypiella), potato moth (Phthorimaea operacule)
lla), Stomopteryx sp. Carposa nipon (Carposina nipon)
Engas and other sink moths, Iraga (Monema)
Iraga species such as flavescens, Chilo supressalis, Cnaphalocross medical
is), Ostrinia nubilalis, and Acorn borer (Ostrinia furnacalis)
, Hellula undal
is), Honey hemlock (Galleria marillone)
lla), Elasmopalpus lignose
llus, Loxostage sticticali
Common moths such as s, Pieris ra (Pieris ra)
Pae), butterflies such as
otis selenaria) and other oak moths, Obicareha (Malacosoma neustria) and other caryoga, Manduca sexta and other sphagnum moths, and Euphortis pseudo
conspersa), gypsy moth (Lymantri)
a dispar) and the like, Hypotria cunea and other tobacco triggers, and tobacco budworms (Heliothis vir)
escens), ball worm (Helicoverp)
a zea), Spodoptera (Spodopte)
raexigua), Helicover
rpa armigera), Spodoptera litura (Spo)
doptera litura), Spodoptera frugiperda (Mame)
stra brassicae), Tamanayaga (Agr)
otis ipsiron), armyworm (Pseud)
algae such as aletia separa) and nettle peach (Trichoplusia ni).

Pests of the order Coleoptera, such as the hemlock buoy (A
Nomala cuprea, Japanese beetle (Popi)
llia japonica), Japanese beetle (Anom)
ala rufocuprea), Eutheola
Scarab beetles such as rugieps, wireworms (Agriotes sp.), Conodeus s
p. Click beetles such as
pilachna vignioctopunct
ata), green ladybird (Epilachna)
varivestis) and other ladybirds, Tribium castaneu
m) etc., Tenebrionidae, stag beetle (Ano
Plophora malasiasia), Pine horned beetle (Monochamus alternat)
us) and other beetles, common bean weevil (A)
canthoscelides obtectus),
Azuki bean weevil (Callosobruchus ch
inensis and other bean weevils, Colorado potato beetle (Leptinotarsa decemlineat)
a), Corn root worm (Diabroticas)
p. ), Oedema oryza (Oulema oryza)
e), the beetle Beetle (Chaetocnema)
concinna), Phaedon cochlea
rias, Oulema melanopus, Dic
Chrysomelidae such as ladispa armigera, Ap
Weevil weevil (Lionthorptus oryz) such as ion godmani
opilius), Boll Weevil (Anthonom)
weevil such as us grandis, weevil such as weevil (Sitophilus zeamais), bark beetles, beetles, beetles and the like.

Diptera pests, such as, for example
ipra ano), rice chironomid (Tanytars)
us oryzae), rice cinnamome fly (Ors)
eolia oryzae), fruit fly (C
eratitis capitata), rice flesh fly (Hydrellia griseola), sweet fruit fly (Drosophila suzu)
kii), Fritz fry (Oscinella fr)
it), rice fly (Chlorops oryza)
e), common bean flies (Ophiomyia ph)
aseoli), bean leafhopper (Liriomyz)
a trifolii), Pleurotus cornucopiae (Pe
gomya hyoscyami), fly (Hyl)
emiaplatura), sorghum fry (Athe)
Rigona soccata, Housefly (Musc)
a domestica), botfly (Gastrop)
hilus sp. ), Fly (Stomoxys)
sp. ), Aedes aegypt
i), Culex pipiens, Anopheles slennesi
s), Culex tritaen
iorhynchus) etc.

Hymenoptera pests, for example, honeybees (Ceph)
us sp. ), Anterior wasps (Harmolit)
a sp. ), Turnip bees (Athalia s)
p. ), Wasps (Vespa sp.), Fire ants and the like.

Orthoptera pests such as German cockroach (B
latera germanica), American cockroach (Periplaneta americana)
), Kera (Gryllotalpa african)
a), grasshopper (Locustamigratoria)
migratriodes), Melanoplus
sanguinipes and the like.

Termite pests, for example, Reticulitermes speratus,
Yellow termites (Coptothermes formos)
anus) etc.

Pests of the thrips order, for example, Thrips thrips dorsal
is), Thrips palmi Thrips pa
lmi), croton thrips (Heliothrip)
s haemorrhoidalis), orange thrips (Frankliniella occid)
entalis), rice thrips (Haplot)
rips auretus) etc.

Mite species, such as the spider mite (Tetra)
nychus urticae), Kanzawa spider mite (T
etranychus kanzawa), citrus red mite (Panynychus citri), apple mite (Panynychusulmi), yellow mite (Eotetranychus carpini),
Texas Citrus Might (Eotetranychus)
banksi), citrus rust mite (Phylloco)
Ptruta oleivora), Polyphagota sononemus latu
s), Red Mite (Brevipalpus s)
p. ), Robin Dite (Rhizoglyphus r
obini), Plutella xylostella (Tyrophagus)
putrescentiae) and the like.

Plant parasitic nematodes, for example, Meloidogyne incogn
ita), Negusaaresenchu (Pratylench)
ussp. ), Soybean cyst nematode (Hetero)
dera glycines), rice garlic nematodes (Aphelenchoides bessey)
i), Bursaphelen
chus xylophilus) and the like.

Other pests, unpleasant animals, sanitary pests, and parasites, for example, Pomacea ca
naliculata), slugs (Incilari)
asp. ), African Maimai (Achatina f
Gastropoda, such as Ulica),
Pill bug (Armadillidium sp.),
Walleye bug, centipede and other isopods (Isopoda),
Liposcelis sp. Etc., C, etc.
tenolepisma sp. Spots such as Pule
x sp. , Ctenocephalides sp.
Fleas such as Trichodectes sp. Hazels such as Cimex sp. And other bed bugs, Boophilus microplus
s), Haemaphysalis
long-lived mites such as longicornis) and Dermatophagoides farinae can be mentioned.

Further, it is also effective against organic phosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, acylurea compounds or harmful insects which are resistant to existing insecticides.

Next, the formulation method will be specifically described with reference to representative formulation examples. The kinds and compounding ratios of the compound and the auxiliary agent are not limited to these and can be changed in a wide range. In the following description,% indicates weight percentage.

Formulation Example 1 Emulsion Compound (I-22) 30%, cyclohexanone 20%,
Polyoxyethylene alkyl aryl ether 11%,
An emulsion was prepared by uniformly dissolving 4% calcium alkylbenzene sulfonate and 35% methylnaphthalene.

Formulation Example 2 Wettable Powder Compound (I-22) 10%, naphthalenesulfonic acid formalin condensate sodium salt 0.5%, polyoxyethylene alkylaryl 0.5%, diatomaceous earth 24%, clay 6
5% was uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 3 Dust: 2% of compound (I-22), 5% of diatomaceous earth and 93% of clay.
Was uniformly mixed and pulverized to obtain a powder.

Formulation Example 4 Granules Compound (I-22) 5%, lauryl alcohol sulfate sodium salt 2%, sodium lignin sulfonate 5%, carboxymethylcellulose 2% and clay 8
6% was uniformly mixed and ground. 20 parts by weight of water was added to 100 parts by weight of this mixture, and the mixture was kneaded.
It was processed into granules of 4 to 32 mesh and then dried to obtain granules.

Next, the effects of the pest control agent containing the compound of the present invention as an active ingredient will be described with reference to test examples. The comparative agents a and b used are those disclosed in JP-A-54-54.
The compounds of [Example 165] and [Example 6] exemplified in the specification of Japanese Patent No.
The compound of [Example 88] exemplified in the specification of 6-45452, and the comparative drug d is USP 3,732.
307 is the compound of [Example 6]. These were formulated and used in the same manner as the compounds of the present invention.

Comparative drug a: 4-chloro-4'-isopropylthiobenzophenone-N'-ethoxycarbonylhydrazone Comparative drug b: 4-chloro-4'-propylsulfonylbenzophenone-N'-propionylhydrazone Comparative drug c: 4- Chloro-4'-methylsulfinylbenzophenone-N'-ethoxycarbonylhydrazone Comparative drug d: 4-trifluoromethylthiobenzophenone hydrazone

Test Example 1 Diamondback moth insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Cabbage leaves were dipped in the solution, air-dried, and then placed in a vinyl chloride cup having a volume of 60 ml. Ten third-instar larvae of Plutella xylostella were released therein and the lid was closed. afterwards,
It was placed in a constant temperature room at 25 ° C., and 6 days later, the number of dead insects was examined, and the dead insect rate was calculated by the following formula 1. The results are shown in Tables 36 to 43. In addition, the test was conducted in two consecutive systems.

[0264]

[Equation 1]

[0265]

[Table 36]

[0266]

[Table 37]

[0267]

[Table 38]

[0268]

[Table 39]

[0269]

[Table 40]

[0270]

[Table 41]

[0271]

[Table 42]

[0272]

[Table 43]

Test Example 2 Black-necked planthopper insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Rice foliage was soaked in the drug solution, air-dried, and then allowed to stand in a test tube. Five brown planthopper larvae in it
The head was released and plugged with absorbent cotton. Then, it was placed in a constant temperature room at 25 ° C., and 6 days later, the number of dead insects was examined, and the dead insect rate was calculated by the equation 1. The test was conducted in two consecutive cycles. The results are shown in Table 44 to Table 4.
8 shows.

[0274]

[Table 44]

[0275]

[Table 45]

[0276]

[Table 46]

[0277]

[Table 47]

[0278]

[Table 48]

Test Example 3 Azuki beetle insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 100 ppm. The chemical solution 0.75ml volume 60ml
Was dropped onto a 6 cm diameter filter paper placed in a vinyl chloride cup. Five female adzuki bean weevils were released in the cap and the lid was closed. Then, it was placed in a constant temperature room at 25 ° C., and four days later, the number of dead insects was investigated, and the dead insect rate was calculated by the equation 1. The test was conducted in two consecutive cycles. The results are shown in Tables 49 to 50.

[0280]

[Table 49]

[0281]

[Table 50]

[0282]

INDUSTRIAL APPLICABILITY The compound of the present invention comprises a hemiptera pest, a lepidopteran pest, a coleopteran pest, a dipteran pest, a hymenoptera pest, an orthoptera pest, a termite pest, a thrips pest, a spider mite, It shows an excellent control effect against a wide range of pests such as plant parasitic nematodes, and can also control pests with resistance.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 303/34 C07C 303/34 311/27 311/27 311/30 311/30 311/35 311/35 315 / 04 315/04 317/16 317/16 317/24 317/24 319/20 319/20 323/16 323/16 323/22 323/22 323/29 323/29 (72) Inventor Nao Masuyama Iwata, Shizuoka Prefecture 408 Shio-shinta, Fukuda-cho, Gunma 1 Keio Research Institute, Inc. (72) Inventor Akihide Nagai 1 408, Shio-shinta, Fukuda-cho, Iwata-gun Shizuoka Kai Research Institute, Inc. (72) Inventor Yano Yuko 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka (72) Inventor Mieko Kawashima 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka (72) Inventor Hiroshi Kurihara 5-120-5205 Nakahira, Tenpaku-ku, Aichi Prefecture (72) Tomonori Shimazu 48, 6-10 Sanarudai, Hamamatsu City, Shizuoka Prefecture

Claims (7)

[Claims] 1. A compound represented by the general formula [I]:{In the formula, R¹Is an alkyl group having 1 to 6 carbon atoms, 1 carbon atom
To C4 cyanoalkyl groups, C1 to C4 hydroxy
Sialkyl group, cycloalkyl group having 3 to 6 carbon atoms, charcoal
Haloalkyl group having 1 to 6 primes, Al having 2 to 4 carbons
Kenyl group, alkynyl group having 2 to 4 carbon atoms, phenyl group
[The group is a halogen atom or an alkyl group having 1 to 4 carbon atoms.
May be substituted with], a cyano group, a benzyl group [wherein
May be substituted with halogen atom], thiazolyl group, charcoal
Alkylcarbamoyl group having a prime number of 1 to 4 or -N
(R⁵) R⁶Group, R²And R³Each independently water
Elementary atoms, halogen atoms, cyano groups, carbon atoms of 1 to 4
Rualkyl group, haloalkyl group having 1 to 3 carbon atoms, 1 carbon atom
To C4 alkylthio groups, C1 to C4 alkyl groups
Rubonyl group, carboxyl group or alkenyl group having 1 to 4 carbon atoms
Indicates a coxycarbonyl group. R²And R³Is these conclusions
A 3- to 6-membered ring may be formed with the combined carbon atom.
Also, R¹And R²Is these bound sulfur atom and carbon
3 having one or more heteroatoms with the atom
To form an 8-membered ring. R⁴Is hydrogen atom, halogen
Atoms, alkyl groups having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Haloalkyl group, C1-C4 alkoxy group or carbon
R is a haloalkoxy group having a prime number of 1 to 4 and R⁵And R⁶
Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Alternatively, it represents a haloalkyl group having 1 to 4 carbon atoms. Also, R⁵
And R⁶Group together = CR⁷R⁸Forming or R⁵
And R⁶Is one together with these bonded nitrogen atoms
Or forming a 4- to 8-membered ring having more heteroatoms
May be. R⁷Is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms
R 1 or an alkylthio group having 1 to 3 carbon atoms, R⁸
Is an alkylthio group having 1 to 3 carbon atoms or 1 to 3 carbon atoms
Is an alkylamino group. Also, R⁷And R⁸Are these
Saturated or unsaturated with combined carbon atom of 4
To form an 8-membered ring. A is a formula [A1] or a formula
[A2]A hydrazino aralkyl group or hydrazonoara
A alkyl group;⁹Is hydrogen atom, halogen atom, nit
B group, cyano group, alkyl group having 1 to 4 carbon atoms, carbon number
1 to 4 haloalkyl group, 1 to 4 carbon atoms
Si group, haloalkoxy group having 1 to 4 carbon atoms, 1 carbon atom
4 alkylthio groups, haloalkyl having 1 to 4 carbon atoms
Thio group, alkylsulfonyl group having 1 to 4 carbon atoms, carbon
Alkylsulfonylmethyl group having 2 to 4 carbon atoms or 1
4 haloalkylsulfonyloxy group, phenyl group
[The group may be substituted with a halogen atom] or pheno
A xy group, which may be substituted with a halogen atom.
You. Also, two R⁹To form a 5- to 6-membered ring
Good. R¹⁰Is a hydrogen atom or an alkane having 1 to 4 carbon atoms
A kill group;¹¹, R¹²And R¹³Are independent
Hydrogen atom, cyano group, alkyl group having 1 to 6 carbon atoms,
C1-C4 haloalkyl group, C2-C10
Alkoxyalkyl groups, C3 to C8 alkoxy groups
Lucoxyalkyl group, C2-C6 alkylthioa
Rukyl group, alkenyl group having 2 to 6 carbon atoms, 2 carbon atoms
Alkynyl group of 4 or the like, cyanoalkyl having 1 to 4 carbon atoms
Group, benzyl group [the group is a halogen atom, having 1 to 4 carbon atoms]
With a haloalkyl group or an alkyl group having 1 to 4 carbon atoms
May be replaced], group -COR¹⁴, Group-CSR¹⁴,
Group -COOR¹⁵, Group-COSR¹⁵, Group -CON (R
¹⁶) R¹⁷, Group-CSN (R¹⁶) R¹⁷, Group-SN
(R¹⁸) R¹⁹, Group-SO₂R²⁰Or the group -C (R
²¹) = CHR²²Is shown. Also, R¹²And R¹³Haichi
It's a group, CR²³R²⁴Or R¹²as well as
R13 is one or more together with these bonded nitrogen atoms.
Form a 4- to 8-membered ring with more heteroatoms
May be. R¹⁴Is a hydrogen atom, an alkane having 1 to 20 carbon atoms
Kill group, haloalkyl group having 1 to 8 carbon atoms, 2 carbon atoms
12 alkoxyalkyl groups, C2-10 ha
Ralkoxyalkyl group, alkoxy having 3 to 16 carbon atoms
Sialkoxyalkyl group, C4 to C22 alkoxy
Cyalkoxyalkoxyalkyl group having 3 to 6 carbon atoms
Cycloalkyl group, hydroxyalkyl having 1 to 6 carbon atoms
Ru group, aminoalkyl group having 1 to 6 carbon atoms, 1 carbon number
6 amidoalkyl groups, cyanoal having 1 to 8 carbon atoms
Kill group, alkoxycarbonylal having 3 to 12 carbon atoms
Kill group, C2-C6 alkenyl group, C2-C2
4 alkynyl group, phenyl group [wherein the group is a halogen atom,
Nitro group, C1-4 alkyl group, C1
4 haloalkyl group, phenoxy group or 1 to 4 carbon atoms
May be substituted with an alkoxy group of], a naphthyl group [
Substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms
Or a heteroaromatic ring group [wherein said group is a halogen atom]
Child, may be substituted with an alkyl group having 1 to 4 carbon atoms]
And R¹⁵Is an alkyl group having 1 to 20 carbon atoms, carbon
A haloalkyl group having 2 to 8 carbon atoms, an alkyl group having 2 to 12 carbon atoms
Coxyalkyl group, alkenyl group having 2 to 6 carbon atoms, charcoal
Alkynyl group and benzyl group having a prime number of 2 to 4 [the group is a halo
Gen atom, alkoxy group having 1 to 4 carbon atoms or 1 carbon atom
To 4 alkyl groups] or phenyl
A group [the group may be substituted with a halogen atom],
R¹⁶Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Then R¹⁷Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or
Is a phenyl group [which is a halogen atom, having 1 to 4 carbon atoms
Placed with a haloalkoxy group or an alkyl group having 1 to 4 carbon atoms
May be replaced) and R¹⁸And R¹⁹Are independent
And an alkyl group having 1 to 4 carbon atoms (the group having 1 to 4 carbon atoms
4 may be substituted with an alkoxycarbonyl group of 4], charcoal
An alkoxyalkyl group having a prime number of 2 to 5 is shown. Also, R
¹⁸And R¹⁹Together with these bound nitrogen atoms
A 5- to 6-membered ring may be formed. R²⁰Is from 1 carbon
A 4-alkyl group, a haloalkyl group having 1 to 4 carbon atoms, or
A dialkylamino group having 2 to 4 carbon atoms, R²¹Is
A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R
²²Is an alkanoyl group having 2 to 4 carbon atoms or 2 carbon atoms
6 represents an alkoxycarbonyl group, and R²³And R
²⁴Are independently hydrogen atom, halogen atom, carbon number
1 to 6 alkyl groups or groups -N (R²⁵) R²⁶Shows
Then R²⁵And R²⁶Are independently hydrogen atom and carbon
Alkyl group having 1 to 4 carbons, Alkoxy having 1 to 4 carbons
Group, an alkoxyalkyl group having 2 to 12 carbon atoms or a group-
SO₂R²⁷Is shown. Also, R²⁵And R²⁶Are these
Even if it forms a 5- to 6-membered ring together with the bonded nitrogen atom,
Good. R²⁷Is an alkyl group having 1 to 8 carbon atoms or phenyl
Group [which is a halogen atom or an alkyl group having 1 to 4 carbon atoms]
May be substituted with a group], Q¹And Q²Is nitrogen
Atom or group-CR⁹And m is an integer of 1 or 2 to 3.
, N is 0, 1 or 2. } Benji represented by
Rusulfide derivatives and salts thereof. 2. A compound represented by the general formula [II]: {In the formula, R ¹ , R ² , R ³ , R ⁴ and n have the same meanings as described in claim 1, and B is the formula [B1] or the formula [B
2] Represents an aralkyl group or an arylcarbonyl group represented by, R ⁹ , R ¹⁰ , m, Q ¹ and Q ² have the same meanings as described in claim 1, and R ²⁸ represents a halogen atom or a hydroxyl group. } The benzyl sulfide derivative represented by these. 3. A compound represented by the general formula [III]: {In the formula, R ⁴ , R ⁹ , R ¹² , R ¹³ , m, Q ¹ and Q
² has the same meaning as in claim 1, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁹ represents a halogen atom, a mercapto group or a hydroxyl group. . } The benzophenone hydrazone derivative represented by these. 4. A compound represented by the general formula [IV]: {In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , m, n, and Q ¹
And Q ² have the same meanings as in claim 1. } And a compound represented by the general formula [V1], {In the formula, R ¹² and R ¹³ have the same meanings as described in claim 1. } The method for producing a benzyl sulfide derivative according to claim 1, wherein A is the formula [A2]. 5. A compound represented by the general formula [III]: {In the formula, R ² , R ³ , R ⁴ , R ⁹ , R ¹² , R ¹³ and R
²⁹ , m, Q ¹ and Q ² have the same meanings as described in claim 3. } And a compound of the general formula [V2], Z-R ¹ [V2] {wherein Z is a halogen atom or an alkylsulfonyloxy group having 1 to 4 carbon atoms when R ²⁹ is a mercapto group. A group or a benzenesulfonyloxy group [the group may be substituted with a methyl group. ], And when R ²⁹ is a halogen atom, a group-
S (O) nM is shown, and when R ²⁹ is a hydroxyl group, a group -SSR ¹ is shown. R ¹ is an alkyl group having 1 to 6 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or Represents a benzyl group (which may be substituted with a halogen atom), M represents an alkali metal, and n represents 0 or 2. } The method for producing a benzyl sulfide derivative according to claim 1, wherein A is the formula [A2]. 6. A compound represented by the general formula [VI]: {In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ , m,
n, Q ¹ and Q ² have the same meanings as described in claim 1,
R ²⁸ represents a halogen atom. } And a compound represented by the general formula [V1], {In the formula, R ¹² and R ¹³ have the same meanings as described in claim 1. } The method for producing a benzyl sulfide derivative according to claim 1, wherein A is the formula [A1]. 7. A pest control agent containing the benzyl sulfide derivative according to claim 1 as an active ingredient.